JP6402977B2 - Printing agents and fabrics - Google Patents

Description

  The present invention relates to a printing agent and a fabric material particularly suitable for use for printing on a fabric.

  As a printing method for printing images such as characters, pictures, designs, etc. on fabrics such as woven fabrics, nonwoven fabrics, and knitted fabrics, a pigment printing method using water-based pigment ink is known. The pigment printing method is a method in which a printing agent, which is a pigment composition composed of a color pigment and a binder resin, is printed and then fixed to a substrate through a drying and curing step as necessary. As this printing method, a silk screen method (for example, refer to Patent Document 1) in which a pattern of a screen candy is continuously printed on a cloth, or an ink jet recording method in which ink is ejected from a nozzle and adhered to the cloth (for example, refer to Patent Document 2). )It has been known.

  Compared to dye-based printing methods, pigment printing methods do not require the selection of colorants depending on the fiber type, the processing method is simple, and there is no need for steaming, water washing or soaping processes, so there is no energy cost. . Moreover, since no waste liquid is generated, it is a safe processing method in terms of environment. However, the pigment printing method requires a sufficient amount of a binder resin for fixing a pigment in order to obtain fastness such as washing fastness, and sometimes a problem occurs due to this binder resin.

As the pigment fixing binder resin for imparting fastness, water-dispersed resins such as high molecular weight acrylic and urethane are usually used.
In textile printing using a screen, even if a sufficient amount of these high molecular weight binder resins is added, printing can be performed without any problem. However, since the binder resin is easily formed into a film, sometimes the binder resin is dried and fixed, and a water-insoluble resin film is stretched to cause problems such as clogging of the screen flaws. In particular, when it is applied to a photographic pattern having a fine pattern (halftone dot or line), the highlight portion is likely to be clogged because it dries quickly. In addition, when the printing operation is stopped with ink remaining on the plate, the ink dries on the plate, and when the printing operation is resumed, the dried and fixed ink does not easily re-dissolve (this will be referred to as the following). There is a problem that ink transfer is difficult and printing cannot be performed.

  On the other hand, since the ink jet recording method is a printing method in which an ink droplet is ejected from a very thin nozzle of several tens of μm to record an image, dry fixing of the ink at the nozzle tip directly affects the ejection stability. .

  On the other hand, as an ink excellent in ejection stability and detergency, for example, in Patent Document 3, the content of the free polymer derived from the water-insoluble polymer in the ink is 1.0% by mass or less with respect to the total mass of the ink. An aqueous pigment composition is disclosed in which the wetting agent is at least one selected from urea, urea derivatives, pyrrolidone derivatives, alkylglycine or glycylbetaine, and saccharides. However, when the ink is applied to textile printing as an ink for textile printing, it has been difficult to obtain fastness. In addition, inks containing a large amount of binder resin in order to obtain sufficient fastness have a problem that the ink viscosity becomes too high and the discharge itself is difficult, and a specific material such as urea is required to ensure the discharge stability. There was a problem that storage stability deteriorated by adding too much wetting agent.

  Further, regarding a pigment printing method using an ink jet recording method, Patent Document 4 discloses an aqueous pigment 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 includes a pigment that can be dispersed in water by coating with a polymer layer containing fine resin particles, the dispersion has an average particle diameter of 20 to 300 nm, and the polyurethane resin is a constituent component. An aqueous pigment composition for ink jet recording, which comprises a compound represented by the following formula (I) or / and formula (II) and excellent in fastness and ejection stability, is disclosed. However, no knowledge about nozzle clogging after a long pause of printing is disclosed.

JP 2007-332523 A JP 2009-215506 A JP 2011-42771 A JP 2011-246634 A

  An object of the present invention is to provide a printing agent excellent in storage stability and re-dissolvability, and a fabric product obtained by printing the printing agent on a fabric.

  The present inventors use a urethane resin having a specific structure as a binder resin, and contain at least one wetting agent selected from the group consisting of urea, urea derivatives, pyrrolidone derivatives, alkylglycines, and saccharides. It has been found that a printing agent excellent in re-solubility can be obtained, regardless of whether it is a silk screen method or an ink jet recording method.

  That is, the present invention includes a pigment, a water-soluble solvent and / or water, a polyester polyol (a1-1) obtained by reacting a polycarboxylic acid and a polyol as the polyol (a1), an anionic group, a cationic group, A urethane resin obtained by reacting a polyol having a hydrophilic group which is a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group with a polyisocyanate (a2), urea, urea derivative, pyrrolidone derivative, alkylglycine, And a printing agent containing at least one wetting agent selected from the group consisting of saccharides.

The present invention also provides a fabric product obtained by printing the above-described printing agent on a fabric.

The present invention also provides a printing method for printing the above-described printing agent on a fabric.

  The printing agent of the present invention contains a urethane resin having a polyester structure and a hydrophilic group in one molecule and at least one wetting agent selected from the group consisting of urea, urea derivatives, pyrrolidone derivatives, alkylglycines, and saccharides. Therefore, it is excellent in storage stability and re-dissolution property. Further, the printing agent of the present invention can be used without any problem whether it is a silk screen method or an ink jet recording method.

(Pigment)
The pigment used in the present invention is not particularly limited, and those usually used as pigments for screen recording inks and water-based inkjet recording inks can be used as colorants. Specifically, known inorganic pigments and organic pigments that can be dispersed in water or water-soluble organic solvents can be used. Examples of the inorganic pigment include carbon black produced by a known method such as titanium oxide, iron oxide, a contact method, a furnace method, and a thermal method. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

Specific examples of the pigment include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Regal 660R, Mull 660R, Mull 660R Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are Degussa's Color Black FW1, FW2, FW2V, FW18, FW200, S170, U, S150, S35, P , V, 1400U, Special Black 6 , 5, 4, 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180, and the like.
Specific examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.
Specific examples of pigments used in magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, etc. Can be mentioned.
Specific examples of pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66, and the like.

  In the present invention, a so-called self-dispersing pigment (surface-treated pigment) having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant may be used. So-called capsule pigments (water-dispersible polymer-containing pigments) that can be stably maintained without a dispersant, or pigments dispersed with a dispersant may be used.

  As the pigment used in the present invention, either dry powder or wet cake can be used. Moreover, these pigments may be used independently and may be used in combination of 2 or more types.

The pigment used in the present invention is preferably a pigment having a particle size of 25 μm or less, and particularly preferably a pigment having a particle size of 1 μm or less. When the particle diameter is within this range, pigment settling hardly occurs and the pigment dispersibility is good.
For the measurement of the particle diameter, for example, a value measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) can be adopted.

(Water-soluble solvent and / or water)
As the water-soluble solvent and / or water used in the present invention, any conventionally used water-based ink for ink jet recording can be used.
Examples of the water-soluble solvent include mono- or polyhydric alcohols, amides, ketones, keto alcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, polyalkylene glycols, glycerin, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1 , 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol and other polyols, Polyhydric alcohol alkyl ethers such as ethylene glycol monobutyl ether and tetraethylene glycol monomethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, and polyhydric alcohol aralkyl ethers, 2-pyrrolidone, Lactams such as N-methyl-2-pyrrolidone and ε-caprolactam, 1,3-dimethylimidazolidinone acetone, N-methyl-2-pyrrolidone, m-butyrolactone, polyoxyalkylene adduct of glycerin, propylene glycol monomethyl ether acetate Dimethyl sulfoxide, diacetone alcohol, dimethylformamide, propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more.

  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 printing agent is stored for a long period of time.

(Urethane resin)
The present invention relates to a polyester polyol (a1-1) obtained by reacting a polycarboxylic acid and a polyol as the polyol (a1), an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group. A urethane resin obtained by reacting a polyol having a hydrophilic group with polyisocyanate (a2) is used. (Hereinafter, this urethane resin is referred to as “urethane resin (A)”)

  Moreover, in this invention, it is essential when using the urethane resin (A) which has a polyester structure with a hydrophilic group in order to solve the subject of this invention.

  The polyester structure is composed of an aliphatic, alicyclic or aromatic structure having an ester bond. It is preferable to use the said polyester structure in 10-90 mass% with respect to the total mass of the polyol (a1) and polyisocyanate (a2) used for manufacture of a urethane resin (A).

  Here, in the printing agent obtained by using the urethane resin (A) having a polyether structure instead of the polyester structure, the storage stability and re-solubility may be lowered.

  The polyester structure is preferably a structure derived from a polyester polyol obtained by an esterification reaction of a polycarboxylic acid and a low molecular weight polyol, and further has an aromatic structure for storage stability and recycling. It is preferable for improving the solubility.

The urethane resin (A) has a hydrophilic group for imparting dispersion stability in the printing agent.
As said hydrophilic group, what is generally called an anionic group, a cationic group, and a nonionic group can be used, but it is preferable to use an anionic group or a cationic group among them.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used. Among them, a carboxylate group partially or wholly neutralized with a basic compound or the like It is preferable to use a sulfonate group in order to maintain good water dispersibility.

  Examples of basic compounds that can be used for neutralizing the carboxyl group or sulfonic acid group as the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, Metal base compounds containing K, Li, Ca and the like can be mentioned, and among these, neutralization with potassium hydroxide or an aqueous solution thereof is particularly preferable in providing environmentally friendly products.

Moreover, as said cationic group, a tertiary amino group etc. can be used, for example.
Examples of the acid that can be used when neutralizing a part or all of the tertiary amino group include formic acid and acetic acid. Moreover, as a quaternizing agent that can be used when quaternizing some or all of the tertiary amino groups, for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.

  The hydrophilic group imparts better water dispersibility when present at 100 mmol / kg to 1200 mmol / kg with respect to the entire urethane resin (A), and has a range of 150 mmol / kg to 1000 mmol / kg. Is more preferable.

  Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among these, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

It is more preferable that the hydrophilic group is present in an amount of 0.5 to 30% with respect to the entire urethane resin (A) to give better water dispersibility, and is in the range of 1 to 20%.

Moreover, the textile printing agent of this invention may use the crosslinking agent (F) mentioned later. When using the said crosslinking agent (F), it is preferable to use what has functional group [X] which can carry out a crosslinking reaction with the functional group which the said crosslinking agent (F) has as said urethane resin (A).
Examples of the functional group [X] include a carboxyl group and a carboxylate group that can be used as the hydrophilic group. The carboxyl group or the like contributes to the water dispersion stability of the urethane resin (A) in the aqueous medium (C), and when they undergo a crosslinking reaction, they also act as the functional group [X], and the crosslinking agent (F) can be partially crosslinked.
When a carboxyl group or the like is used as the functional group [X], the urethane resin (A) preferably has an acid value of 2 to 50, and has an acid value of 5 to 40. More preferably.

The urethane resin (A) can be produced, for example, by reacting a polyol (a1), a polyisocyanate (a2), and, if necessary, a chain extender.
As the polyol (a1), from the viewpoint of imparting a polyester structure to the urethane resin (A), a polyester polyol (a1-1) is used, and from the viewpoint of imparting a hydrophilic group to the urethane resin (A). A polyol having a hydrophilic group is used.

  Examples of the polyester polyol (a1-1) include polyesters obtained by esterification reaction of low molecular weight polyols and polycarboxylic acids, and polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone. Alternatively, these copolyesters can be used.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butane having a molecular weight of about 50 to 300. Aliphatic polyols such as diols, aliphatic cyclic structure-containing polyols such as cyclohexanedimethanol, bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof can be used. .

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic anhydride, naphthalene-2,6-dicarboxylic acid, Naphthalene dicarboxylic acid such as naphthalene-2,7-dicarboxylic acid and naphthalene-1,5-dicarboxylic acid, aromatic polycarboxylic acid such as dimethyl terephthalate and orthophthalic acid, and anhydrides or ester-forming derivatives thereof Can be used.

  As the aromatic structure-containing polyester polyol that can be used as the polyester polyol (a1-1), for example, a combination of the low molecular weight polyol and the polycarboxylic acid that has an aromatic structure in one or both of them is used. Can be manufactured.

  Specifically, the aromatic structure-containing polyester polyol includes aliphatic polyols such as ethylene glycol, diethylene glycol, and 1,4-butanediol, and aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid. What is obtained by carrying out a combination reaction can be used. It can also be produced by reacting an aromatic structure-containing polyol such as bisphenol A with the aliphatic polycarboxylic acid.

  The aromatic polycarboxylic acid is a total of 5 mass% to 100 mass% of one or more selected from the group consisting of the orthophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid and esterified products thereof with respect to the total amount of the polycarboxylic acid. It is preferable to use what is contained in the range of 30% to 100% by weight, more preferably to contain in the range of 50% to 100% by weight. It is more preferable to obtain a printing agent.

  One or more of the orthophthalic acid and phthalic anhydride are preferably used in a total range of 0.5% by mass to 30% by mass with respect to the total amount of the aromatic polycarboxylic acid. More preferably, it is used in the range of 20% by mass, and more preferably in the range of 1% by mass to 8% by mass. One or more selected from the group consisting of naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and esterified products thereof is a total of 70% by mass to 99.5% by mass with respect to the total amount of the aromatic polycarboxylic acid. It is preferably included in the range, more preferably used in the range of 92% by mass to 99% by mass, and more preferably in the range of 80% by mass to 99.5% by mass. It is more preferable when obtaining an agent.

  As the polycarboxylic acid, for example, an aliphatic polycarboxylic acid other than the aromatic polycarboxylic acid may be used in combination, but the aromatic polycarboxylic acid is 90% by mass with respect to the total amount of the polycarboxylic acid. It is preferable to use in the above range, and it is more preferable to use in the range of 95% by mass to 100% by mass.

  The aromatic structure-containing polyol is obtained by esterifying a polyether polyol obtained by adding an alkylene oxide to a bisphenol compound and an aromatic polycarboxylic acid.

  The aromatic structure-containing polyol can be produced by esterifying an alkylene oxide adduct obtained by adding alkylene oxide to a hydroxyl group of a bisphenol compound and an aromatic polycarboxylic acid.

  The alkylene oxide adduct is a polyether polyol in which an alkylene oxide is added to a hydroxyl group of a bisphenol compound, and can be produced by adding an alkylene oxide by a known and conventional method using the bisphenol compound as an initiator.

Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, 4,4-bis (hydroxyphenyl) sulfide, and bis (4-hydroxy can be used phenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) amine, tricyclo [5,2,1,0 ^2,6] decane phenol. Of these, the use of bisphenol A is preferable in terms of improving storage stability and re-solubility.

  As the alkylene oxide that can be added to the hydroxyl group of the bisphenol compound, for example, ethylene oxide, propylene oxide and the like can be used, and it is preferable to use one or more selected from the group consisting of ethylene oxide and propylene oxide.

  As said alkylene oxide adduct, it is preferable to use what 1 mol-20 mol alkylene oxide added with respect to the said bisphenol compound 1 molecule, and what used 1 mol-10 mol alkylene oxide added is used. It is more preferable to use a product to which 2 to 4 moles of alkylene oxide is added, which does not reduce the aromatic ring concentration in the urethane resin, and can be manufactured with excellent storage stability and resolubility. It is further preferable for obtaining a printing agent.

  When manufacturing the said polyetherester polyol, other polyol (a1-2) etc. can also be used in combination with the alkylene oxide adduct of the said bisphenol compound and aromatic polycarboxylic acid.

  Examples of the other polyol (a1-2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3. -Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7- Heptanediol, neopentyl glycol and the like can be used.

  The other polyol (a1-2) is in the range of 1% by mass to 30% by mass with respect to the total mass of the alkylene oxide adduct of the bisphenol compound, the aromatic polycarboxylic acid, and the other polyol (a1-2). May be used.

  The reaction between the polyol and the polycarboxylic acid can be performed by esterifying the hydroxyl group of the polyol and the carboxyl group of the polycarboxylic acid.

  Specifically, the polyol and the polycarboxylic acid can be reacted at normal pressure or reduced pressure in a reaction vessel substituted with an inert gas such as nitrogen in the presence of a catalyst as necessary. The reaction is preferably performed in the range of 100 ° C to 300 ° C.

  Examples of the catalyst include alkali metal or alkaline earth metal acetates, compounds containing zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium, and the like. Among these, it is preferable to use tetraalkyl titanate or tin oxalate effective for transesterification reaction, polycondensation reaction and the like.

  The catalyst is preferably used in the range of 0.005% by mass to 1.0% by mass with respect to the total mass of the various raw materials used in the production of the polyether ester polyol.

The aromatic structure-containing polyester polyol is used so that the aromatic cyclic concentration contained in the total amount of the polyester polyol (a1-1) to be used is 2.5 mol / kg or more, particularly from the viewpoint of storage stability. The aromatic cyclic concentration is more preferably 3.0 mol / kg or more.
In addition, the said polyester polyol (a1-1) is 1 type of polyester polyol of the same kind (here, the same kind shows that parameters, such as the kind of polycarboxylic acid used as a raw material, a polyol, and molecular weight, are the same). Different types (here, “different types” means different types of polycarboxylic acid and polyol as raw materials, and different parameters such as molecular weight). There is no particular limitation.
In addition, what is necessary is just to calculate an aromatic cyclic density | concentration with respect to the total total amount of all the types of polyester polyols used for the aromatic cyclic density | concentration in the case of using multiple types of different polyester polyols.

  As said polyester polyol (a1-1), it is preferable to use what has the number average molecular weight of the range of 200-5000. Especially, as said aromatic structure containing polyester polyol, when improving, it is preferable to use what has a number average molecular weight of 250-3000.

  Moreover, as said hydrophilic group containing polyol, anionic group containing polyol other than above-described polyester polyol (a1-1), a cationic group containing polyol, and a nonionic group containing polyol can be used, for example. Especially, it is preferable to use an anionic group containing polyol or a cationic group containing polyol, and it is more preferable to use an anionic group containing polyol.

As the anionic group-containing polyol, for example, a carboxyl group-containing polyol or a sulfonic acid group-containing polyol can be used.
Examples of the carboxyl group-containing polyol include 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid, 2,2'-dimethylolbutyric acid, 2,2'-dimethylolvaleric acid, and dicarboxylic acids thereof. A carboxyl group-containing polyester polyol obtained by reacting with an acid can be used. Of these, 2,2′-dimethylolpropionic acid is preferably used.

  The carboxyl group-containing polyol is preferably used in the range where the acid value of the urethane resin (A) is 10 to 70, more preferably 10 to 50. In addition, the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said urethane resin (A).

The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility.
Examples of basic compounds that can be used for neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, NaOH, KOH, and LiOH. A metal hydroxide containing etc. can be used. The basic compound is preferably used in the range of basic compound / anionic group = 0.5 to 3.0 (molar ratio) from the viewpoint of improving the water dispersion stability of the resulting coating agent. It is more preferable to use in the range of 0.5 to 2.0 (molar ratio).

Further, as the cationic group-containing polyol, for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule, and a secondary amine. A polyol obtained by reacting with can be used.
It is preferable that a part or all of the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.
Further, the tertiary amino group as the cationic group is preferably partly or entirely quaternized. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably used.

  Further, as the nonionic group-containing polyol, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

  The hydrophilic group-containing polyol is preferably used in the range of 0.3% by mass to 20.0% by mass with respect to the total amount of polyol used for the production of the urethane resin (A).

  As said other polyol, polyether polyol, polyester polyol, polycarbonate polyol etc. can be used other than the said hydrophilic group containing polyol, for example.

  As the polyether polyol that can be used for the other polyols, for example, those obtained by addition polymerization of alkylene oxide using ethylene glycol, propylene glycol or the like as an initiator can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Examples of polyester polyols that can be used for the other polyols include fats obtained by esterifying ethylene glycol, propylene glycol, and the like with polycarboxylic acids such as orthophthalic acid, isophthalic acid, adipic acid, and sebacic acid. Polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as aromatic polyester polyols, aromatic polyester polyols, and ε-caprolactone, copolymerized polyesters thereof, and the like can be used.

  Examples of polycarbonate polyols that can be used for the other polyols include those obtained by reacting carbonates with various polyols, and those obtained by reacting phosgene with bisphenol A and the like. .

  In addition to the above-mentioned other polyols, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1 A relatively low molecular weight polyol such as, 7-heptanediol or neopentyl glycol can also be used.

  Examples of the polyisocyanate (a2) that reacts with the polyol (a1) to form the urethane resin (A2) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate. , Cycloaliphatic diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, aliphatic or aliphatic cyclic structure-containing diisocyanates such as tetramethylxylylene diisocyanate, etc. may be used alone or in combination of two or more. it can. Among these, the use of an aliphatic cyclic structure-containing diisocyanate is more preferable for imparting excellent storage stability and re-solubility.

  The urethane resin (A) is, for example, in the absence of a solvent or in the presence of an organic solvent, the polyol (a1) containing the polyether ester polyol (a1-1) and the polyisocyanate (a2), as necessary. Can be produced by reacting with a chain extender. When the organic solvent is used, it is preferable to remove the organic solvent by a method such as distillation as necessary when the urethane resin (A) is dispersed in the aqueous medium (B).

  Examples of the organic solvent that can be used in producing the urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; Nitriles; dimethylformamide, N-methylpyrrolidone and the like can be used alone or in combination of two or more.

  The reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. It is preferable to carry out in the range, and it is more preferred to carry out in the range of 0.9 to 1.5.

  The chain extender that can be used when producing the urethane resin (A) can be used for the purpose of increasing the molecular weight of the urethane resin (A) and improving storage stability and re-solubility.

  As a chain extender that can be used when the urethane resin (A) is produced, polyamine, other active hydrogen atom-containing compounds, and the like can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neo Glycols such as pentyl glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Such phenols, water and the like can be used.

  The chain extender is, for example, an isocyanate contained in a urethane prepolymer obtained by reacting the polyol (a1) with the polyisocyanate (a2) so that the equivalent of the amino group and active hydrogen atom-containing group of the chain extender It is preferable to use in the range which becomes 1.9 or less (equivalent ratio) with respect to the equivalent of group, and it is more preferable to use in the range of 0.3-1.0 (equivalent ratio).

  The chain extender can be used when the polyol (a1) and the polyisocyanate (a2) are reacted or after the reaction. Moreover, when the urethane resin (A) obtained above is dispersed in the aqueous medium (B) to make it aqueous, the chain extender can also be used.

  The urethane resin (A) obtained by the above method preferably uses a resin having a weight average molecular weight in the range of 5,000 to 100,000 from the viewpoint of storage stability, and 6,000 to 80,000. It is more preferable to use those having a weight average molecular weight in the range of.

  Moreover, when manufacturing the said urethane resin (A), a hardening accelerator can be used in combination from a viewpoint of reaction time shortening.

  As the curing accelerator, for example, a tertiary amine catalyst or an organometallic catalyst can be used. As the tertiary amine catalyst, for example, triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N, N-dimethylethanolamine, ethylmorpholine and the like can be used. Examples of the organometallic catalyst that can be used include stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, and sodium bicarbonate.

  As the urethane resin (A) obtained by the above method, it is preferable to use a urethane resin having a hydrophilic group as described above, but the urethane resin (A) having no hydrophilic group is used. You can also In such a case, it is preferable to use a surfactant described later as one that can contribute to the dispersion of the urethane resin (A). Even when a hydrophilic group-containing urethane resin is used as the urethane resin (A), the same surfactant may be used as necessary from the viewpoint of further improving the water dispersion stability. .

  Examples of such surfactants include nonions such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Surfactants: fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, alkyl diphenyl ether sulfones Anionic surfactants such as acid sodium salts; Cations such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts It can be used system surfactant. Among these, from the viewpoint of improving the dispersion stability of the urethane aqueous composition, it is preferable to use an anionic or nonionic surfactant.

  When using the said surfactant, it is preferable to use in 0.5 mass%-5 mass% with respect to the whole quantity of a urethane resin (A) from a storage stability and a re-dissolution viewpoint.

  Examples of the method of dispersing the urethane resin (A) obtained by the above method in the aqueous medium (B) include the following methods 1 and 2.

  [Method 1] When a hydrophilic group-containing urethane resin is used as the urethane resin (A), a part or all of the hydrophilic group of the urethane resin obtained by the method is replaced with the basic compound as necessary. A method of obtaining an aqueous dispersion of a urethane resin (A) by mixing and stirring an aqueous medium (B) that has been neutralized or quaternized using an alkanol or the like.

  [Method 2] When a urethane resin having no hydrophilic group is used as the urethane resin (A), the urethane resin obtained by the method and a surfactant described later are mixed under stirring conditions. A method of obtaining an aqueous dispersion of a urethane resin (A) by emulsifying and dispersing by introducing an aqueous medium (B) or forcibly emulsifying and dispersing using an emulsifier or the like.

  When the production of the urethane resin (A) is carried out in the presence of an organic solvent, not in the absence of a solvent, the aqueous dispersion of the urethane resin (A) is produced according to the methods 1 and 2 as necessary. It is preferable to remove the organic solvent by a method such as distillation.

  As said aqueous medium (B) used as the solvent of said urethane resin (A), the organic solvent mixed with water and water, and these mixtures are mentioned. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; N-methyl-2-pyrrolidone and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  In both methods 1 and 2, when the urethane resin (A) is dispersed in water in the aqueous medium (B), a machine such as a homogenizer can be used as necessary.

  The urethane resin (A) thus obtained is in a state where the urethane resin (A) is dispersed in an aqueous medium. When adjusting as a printing agent, it is preferable that the urethane resin (A) is in the form of an aqueous dispersion dispersed in an aqueous medium, as described above. At this time, the aqueous medium is contained in the range of 30% by mass to 90% by mass with respect to the total amount of the composition of the urethane resin (A) in order to obtain a printing agent having excellent water dispersion stability. Is preferable.

  The particle size of the aqueous dispersion of the urethane resin (A) is preferably in the range of 5 nm to 1000 nm, more preferably in the range of 10 nm to 400 nm, from the viewpoint of ejectability of the inkjet ink.

  The urethane resin (A) is generally used in the range of 0.3% by mass to 12% by mass with respect to the total amount of the printing agent. 0.6 mass%-9 mass% are preferable, Furthermore, 1.0 mass%-6 mass% are the most preferable.

The ratio of the urethane resin (A) to the pigment may be a ratio in a range usually used for screen recording ink or ink jet recording ink, for example, a ratio of urethane resin to pigment = 1: 3 to 8: 1. Is preferred.
As described above, the fastness is attributed to the molecular weight of the urethane resin used. The higher the molecular weight, the higher the fastness. In addition to this, the amount of binder used also contributes to the fastness. Therefore, in order to obtain higher fastness, it is preferable that the amount of the binder used is larger. In the urethane resin of the present invention, for example, 1: 1 to 8: 1 gives higher fastness. However, excessive use of a high molecular weight binder resin leads to an increase in viscosity. Therefore, when applied to ink for ink jet recording, it is preferable to determine the amount of binder used in consideration of the balance with viscosity.

(Wetting agent)
The printing agent of the present invention comprises at least one selected from urea, urea derivatives, pyrrolidone derivatives, alkylglycines represented by the general formula (1) described later, and saccharides. The wetting agent is preferably a solid wetting agent. In the present invention, the wetting agent means a water-soluble compound having a water retention function and solid at 25 ° C.

  Examples of the urea derivative include a compound in which hydrogen on nitrogen of urea is substituted with an alkyl group or alkanol, thiourea, a compound in which hydrogen on nitrogen of thiourea is substituted with an alkyl group or alkanol, and the like. Specific examples include N-methylurea, N, N-dimethylurea, thiourea, ethyleneurea, hydroxyethylurea, hydroxybutylurea, ethylenethiourea, and diethylthiourea.

  Examples of the pyrrolidone derivative include compounds in which hydrogen on nitrogen of pyrrolidone is substituted with an alkyl group or an alkanol, specifically, 2-methylpyrrolidone, N-methylpyrrolidone, N-octylpyrrolidone, N- Examples thereof include lauryl pyrrolidone and β-hydroxyethyl pyrrolidone.

The alkyl glycine is represented by the general formula (1).

In general formula (1), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, and M represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. .
Examples of alkyl glycines include N-methyl glycine, N, N-dimethyl glycine, N, N, N-trimethyl glycine, N-ethyl-N-methyl glycine, N, N-diethyl glycine, N-isopropyl-N- Examples include methyl glycine, N-isopropyl-N-ethyl glycine, N, N-diisopropylglycine, N, N-dibutyl glycine, N-butyl-N-methyl glycine, and N-butyl-N-ethyl glycine. .

  Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Specifically, glucose, mannose, fructose, ribose, xylose, arabinose, galactose, Examples include aldonic acid, glucitol, (sorbit), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature, such as alginic acid, α-cyclodextrin, and cellulose.

  In addition, examples of derivatives of these saccharides include reducing sugars (for example, sugar alcohols) and oxidized sugars (for example, aldonic acid, uronic acid, amino acids, thio sugars, etc.) of the aforementioned saccharides. In particular, sugar alcohol is preferable, and among them, maltitol, sorbitol, inositol or xylitol is preferable.

  Since these wetting agents have high hydrogen bonding properties, they are highly effective in preventing ink drying. For this reason, it is considered that inks containing these are less likely to evaporate moisture even in a low humidity environment and are excellent in re-dissolvability.

  The content of the wetting agent in the printing agent of the present invention is preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass with respect to the total mass of the ink. . When the amount of the humectant is less than 0.5% by mass, sufficient resolubility tends not to be obtained. On the other hand, when the amount is more than 20% by mass, the fastness of the printed product tends to be lowered.

  In the present invention, the ratio of the urethane resin (A), which is the binder resin in the textile printing agent, to the wetting agent (the mass of the binder resin / the mass of the wetting agent) is preferably 0.01 to 2.0. It is more preferably 1 to 2.0, and most preferably 0.1 to 1.0.

(Printing agent manufacturing method)
The textile printing agent of the present invention creates a high-concentration aqueous dispersion (pigment paste) of the pigment, dilutes it with a water-soluble solvent and / or water, and adds the urethane resin (A) and other additives as necessary. It can be prepared as an aqueous pigment composition to which an agent has been added.

The method for obtaining the pigment paste by dispersing the pigment in the water-soluble solvent and / or water is not particularly limited, and it is preferable to use a known dispersion method. The dispersant used at this time may be dispersed in water using a known pigment dispersant, or a surfactant may be used.
The pigment dispersant is preferably an aqueous resin, and preferable examples include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid. Styrene such as acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer Examples thereof include acrylic resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
The compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine. The amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
Of course, it is also possible to use a commercial item. As a commercially available product, Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, Ciba Specialty Chemicals EFKA series, etc. can be used.

Moreover, as a dispersion method, the following (1)-(3) can be shown, for example.
(1) A method of preparing a pigment paste by adding a pigment to an aqueous medium containing a pigment dispersant and water and then dispersing the pigment in the aqueous medium using a stirring / dispersing device.
(2) The pigment and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is then mixed using a stirring / dispersing device. A method of preparing a paste.
(3) After adding a pigment to a solution obtained by dissolving a pigment dispersant in an organic solvent compatible with water such as methyl ethyl ketone and tetrahydrofuran, the pigment is added to the organic solution using a stirring / dispersing device. And then phase-emulsifying using an aqueous medium, and then the organic solvent is distilled off to prepare a pigment paste.

The kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, and a planetary mixer.
Also, the stirring / dispersing device is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
One of these may be used alone, or two or more devices may be used in combination.

  The amount of pigment in the pigment paste is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass. When the pigment amount is less than 5% by mass, the water-based ink prepared from the pigment paste is insufficiently colored, and a sufficient image density tends not to be obtained. On the other hand, when the amount is more than 60% by mass, the dispersion stability of the pigment tends to decrease in the pigment paste.

  Further, since coarse particles cause nozzle clogging and other image characteristics to deteriorate, it is preferable to remove coarse particles by centrifugation or filtration before and after ink preparation.

  After the dispersion step, an impurity removal step by ion exchange treatment or ultrafiltration treatment may be performed, followed by post treatment. Ion exchange treatment can remove ionic substances such as cations and anions (divalent metal ions, etc.), and by ultra-treatment, impurities dissolved substances (residual substances during pigment synthesis, excess components in dispersion composition) , Resin not adsorbed to the organic pigment, mixed foreign matter, etc.) can be removed. In the ion exchange treatment, a known ion exchange resin is used. The ultratreatment uses a known ultrafiltration membrane and may be either a normal type or a double capacity up type.

  After preparing the pigment paste, it is appropriately diluted and an additive as required is added to obtain a printing agent according to the purpose. The printing agent of the present invention can be preferably used as a printing agent. In this case, the form of the printing agent is arbitrarily selected according to a preferable processing method such as dip dyeing or printing according to the fiber to be colored. For example, in screen recording inks suitable for textile printing, preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. are used as additives. The final pigment concentration is preferably in the range of 1 to 10% by mass. In such a case, the additive is preferably added together with the binder resin.

  In addition, for example, in the case of a printing agent for dip dyeing, additives include preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, and binder resins. The final pigment concentration is preferably in the range of 1-10% by weight. The viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa · s to 100 mPa · s. In addition, for example, the use of a printing agent for spray printing uses a binder resin as a viscosity modifier, a pH adjuster, a chelating agent, a plasticizer, an antioxidant, an ultraviolet absorber, etc. as an additive. The pigment concentration is preferably in the range of 1 to 10% by mass. The viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa · s to 100 mPa · s.

  In addition, for example, in an inkjet recording ink suitable for textile printing, as additives, preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. The final pigment concentration is preferably 1 to 20% by mass in order to obtain a sufficient image density and to ensure the dispersion stability of the pigment in the ink. In such a case, the additive is preferably added together with the binder resin. The dilution rate can be adjusted for ink jet recording ink by taking into account the concentration of the surfactant aqueous solution, diluting to the required concentration, and then performing ultrasonic treatment.

  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 viscosity modifier include mainly water-soluble natural or synthetic polymers such as carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic, and starch.

  Specific examples of the pH adjuster include collidine, imidazole, phosphoric acid, 3- (N-morpholino) propanesulfonic acid, tris (hydroxymethyl) aminomethane, boric acid and the like.

  Specific examples of chelating agents include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramildiacetic acid, Examples include 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid and salts thereof (including hydrates).

  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.

  The method for adding the diluent and additives can be carried out by a generally used method without any particular limitation. For example, the pigment paste is mixed with a binder resin, a surfactant, a viscosity modifier, an antifoaming agent, an antioxidant or an ultraviolet absorber, an antiseptic, and the like as additives. Examples thereof include a method of dispersing and mixing using a machine or a stirrer such as a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, an ultrahigh pressure homogenizer, or a pearl mill. If necessary, various additives may be further added thereafter.

  In addition, a water-soluble organic solvent may be further added for the purpose of stably dissolving or dispersing the additive, the pigment, the pigment dispersant, and the urethane resin.

  Examples of the water-soluble solvent include mono- or polyhydric alcohols, amides, ketones, ketoalcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, polyalkylene glycols, and glycerin. N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2- Pentanediol, 1,2 Polyols such as 6-hexanetriol, trimethylolpropane, pentaerythritol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene Polyhydric alcohol alkyl ethers such as glycol monobutyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, and polyhydric alcohol aralkyl ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone , Ε-caprolactam and other lactams, 1,3-dimethyli Midazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone, m-butyrolactone, polyoxyalkylene adduct of glycerin, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolane, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, di Acetone alcohol, dimethylformamide propylene glycol monomethyl ether, and the like. These may be used alone or in combination of two or more.

  Further, the printing agent of the present invention may contain a surfactant in order to control its permeability. The surfactant used in this case is preferably one having good compatibility with other components present in the printing agent of the present invention. Further, a surfactant having high penetrability and stability is preferable.

Specifically, it is preferable to use amphoteric surfactants and nonionic surfactants.
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. These surfactants are preferred when added to printing agents 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 wt% or more and 10 wt% or less with respect to the total amount of the printing agent, and a more preferable upper limit value is 5.0 wt%, and a preferable lower limit value is 0.5% by weight.

  Furthermore, when the textile printing agent of the present invention is applied to the ink jet recording method, the surface tension is preferably adjusted to 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, there is a tendency that the non-absorbing base material is easily repelled. The viscosity is preferably 1.2 mPa · s or more and 20.0 mPa · s or less, more preferably 2.0 mPa · s or more and less than 15.0 mPa · s, and further preferably 3.0 mPa · s or more and 12 or more. Less than 0.0 mPa · s. When the viscosity is within this range, it is possible to achieve excellent dischargeability and good jetability over a long period of time. The surface tension can be appropriately adjusted by the surfactant.

(Adherent)
When the printing agent obtained by the production method of the present invention is used as various inks, printing can be performed not only on general-purpose adherends such as paper but also on fabric, artificial leather, natural leather and the like. Particularly excellent for printing on fabrics.
The fabric used in the present invention is preferably a medium composed of fibers, and may be a non-woven fabric or a non-woven fabric. As the material, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, or rayon can be used.

  Hereinafter, although the effect of the present invention is concretely explained using an example and a comparative example, the present invention is not limited to these examples. In the following description, parts and% indicate parts by mass.

<Preparation of polyester polyol>
(Synthesis Example 1)
While introducing nitrogen gas in a reactor equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 69.7 parts by mass of adipic acid, 49.8 parts by mass of butanediol and 0.05 part by mass of dibutyltin oxide were charged 180. After esterification at ˜230 ° C. for 24 hours, a polycondensation reaction is performed at 230 ° C. for 24 hours until the acid value becomes 1 or less, to obtain an aliphatic polyester polyol (PES-1) [acid value 0.3, hydroxyl value 56.1. An aromatic cyclic concentration of 0 mol / Kg] was obtained.

In addition, the said acid value is the value produced by titrating according to the potassium hydroxide method, and a hydroxyl value is the value measured by the method based on JISK1557-1 description.

(Synthesis Example 2)
While introducing nitrogen gas in a reactor equipped with a thermometer, nitrogen gas inlet tube, and stirrer, 42.1 parts by mass of isophthalic acid, 21.4 parts by mass of sebacic acid, 9.3 parts by mass of adipic acid, ethylene glycol 7 7 parts by mass, 25.8 parts by mass of neopentyl glycol, 11.2 parts by mass of butanediol, and 0.05 parts by mass of dibutyltin oxide were esterified at 180 to 230 ° C. for 24 hours, and the acid value was reduced to 1 or less. A polycondensation reaction was performed at 230 ° C. for 24 hours until an aromatic polyester polyol (PES-2) [acid value 0.3, hydroxyl value 56.1, aromatic cyclic concentration 2.53 mol / kg] was obtained.

(Synthesis Example 3)
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 33.0 parts of isophthalic acid, 33.0 parts of terephthalic acid, 23.5 parts of butanediol, 27.2 of neopentyl glycol And 0.04 part of dibutyltin oxide were added, and a polycondensation reaction was performed at 230 ° C. for 24 hours until the acid value became 1 or less at 180 to 230 ° C., and an aromatic polyester polyol (PES-3) [acid value 0.2 Thus, a hydroxyl value of 112.2 and an aromatic cyclic concentration of 3.98 mol / Kg were obtained.

芳香族環式濃度（モル／ｋｇ）：合成したＰＥＳ−１〜ＰＥＳ−３に含まれる芳香族環式濃度である。

Aromatic cyclic concentration (mol / kg): Aromatic cyclic concentration contained in synthesized PES-1 to PES-3.

<Preparation of polyether ester polyol>
(Synthesis Example 4)
In a four-necked flask, 336 parts by mass of diethylene glycol, 1039 parts by mass of SEO-2 (2 mol adduct of bisphenol S, manufactured by Nikka Chemical Co., Ltd.), 626 parts by mass of phthalic anhydride, 0.06 mass of tetrabutyl titanate The parts were charged and reacted at 220 ° C. for 24 hours under a nitrogen stream. After the reaction, the resulting polyether ester polyol (PES-4) was a yellow solid at room temperature, having an acid value of 9.23 and a hydroxyl value of 107.7.

(Synthesis Example 5)
Into a four-necked flask, 2167 parts by mass of Newpol-BPE-20T (2 mol adduct of bisphenol A ethylene oxide, manufactured by Sanyo Chemical Industries), 473 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, dimethyl terephthalate 301 Part by mass, 15 parts by mass of phthalic anhydride, and 0.06 parts by mass of tetrabutyl titanate were charged and reacted at 220 ° C. for 24 hours under a nitrogen stream. After the reaction, the resulting polyether ester polyol (PES-5) was a yellow solid at room temperature, having an acid value of 0.08 and a hydroxyl value of 102.0.

(Synthesis Example 6)
A four-necked flask was charged with 3009 parts by weight of Newpol-BPE-20T, 369 parts by weight of isophthalic acid, 540 parts by weight of dimethyl terephthalate, 82 parts by weight of phthalic anhydride, and 0.06 parts by weight of tetrabutyl titanate under a nitrogen stream. , Reacted at 220 ° C. for 24 hours. After the reaction, the obtained polyetherester polyol (PES-6) was a pale yellow solid at room temperature, having an acid value of 0.05 and a hydroxyl value of 111.6.

(Synthesis Example 7)
A four-necked flask was charged with 830 parts by mass of terephthalic acid, 830 parts by mass of isophthalic acid, 374 parts by mass of ethylene glycol, 598 parts by mass of neopentyl glycol, and 0.06 parts by mass of tetrabutyl titanate. Reacted for hours. After the reaction, the obtained polyester polyol (PES-7) was a light yellow solid at room temperature, having an acid value of 0.2 and a hydroxyl value of 74.5.

芳香族環式濃度（モル／ｋｇ）：合成したＰＥＳ−４〜ＰＥＳ−７に含まれる芳香族環式濃度である。

Aromatic cyclic concentration (mol / kg): Aromatic cyclic concentration contained in synthesized PES-4 to PES-7.

Abbreviations in Table 2 will be described below.
Polyether polyol 1; “SEO-2”, manufactured by Nikka Chemical Co., Ltd., bisphenol S ethylene oxide 2-mol adduct Polyether polyol 2; “New Pole-BPE-20T”, manufactured by Sanyo Chemical Industries, Ltd., bisphenol A Ethylene oxide 2-mole adduct of “aromatic ring structure content”; the mass ratio of the aromatic ring structure to the total polyether ester polyol, and calculated based on the raw material charge.

<Synthesis of urethane resin>
(Production Example 1)
In a reaction vessel, 100 parts by mass of the aliphatic polyester polyol (PES-1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 94.1 parts by mass of methyl ethyl ketone was added, stirred and evenly mixed. Mixed. Next, 8.8 parts by mass of 2,2-dimethylolpropionic acid and 4.2 parts by mass of 1,4-butanediol were added, and then 28.1 parts by mass of tolylene diisocyanate and 0.08 parts by mass of dibutyltin dilaurate were added. In addition, the reaction was carried out at 80 ° C. for 12 hours to carry out the urethanization step. It was confirmed that the isocyanate value was 0.1% or less, 0.4 parts by weight of normal butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the nonvolatile content of the urethane resin having a hydrophilic group A 60% by weight solution was obtained.
Then, it is cooled to 50 ° C., 6.7 parts by mass of triethylamine and 710 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition (PUD-1) having a nonvolatile content of 23% by mass in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 2)
In a reaction vessel, 100 parts by mass of the aromatic polyester polyol (PES-2) obtained in Synthesis Example 2 was dehydrated at 100 ° C. under reduced pressure, and after cooling to 80 ° C., 94.1 parts by mass of methyl ethyl ketone was added, stirred and evenly mixed. Mixed. Next, 8.8 parts by mass of 2,2-dimethylolpropionic acid and 4.2 parts by mass of 1,4-butanediol were added, and then 28.1 parts by mass of tolylene diisocyanate and 0.08 parts by mass of dibutyltin dilaurate were added. In addition, the reaction was carried out at 80 ° C. for 12 hours to carry out the urethanization step. It was confirmed that the isocyanate value was 0.1% or less, 0.4 parts by weight of normal butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the nonvolatile content of the urethane resin having a hydrophilic group A 60% by weight solution was obtained.
Then, it is cooled to 50 ° C., 6.7 parts by mass of triethylamine and 710 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition (PUD-2) having a nonvolatile content of 23% by mass in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 3)
In a reaction vessel, 100 parts by mass of the aromatic polyester polyol (PES-3) obtained in Synthesis Example 3 was dehydrated at 100 ° C. under reduced pressure, then cooled to 80 ° C., 91.0 parts by mass of methyl ethyl ketone was added, and the mixture was stirred uniformly. Mixed. Next, 8.1 parts by mass of 2,2-dimethylolpropionic acid was added, then 28.4 parts by mass of tolylene diisocyanate and 0.08 parts by mass of dibutyltin dilaurate were added and reacted at 80 ° C. for 12 hours. The process was carried out. It was confirmed that the isocyanate value was 0.1% or less, 0.4 parts by weight of normal butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the nonvolatile content of the urethane resin having a hydrophilic group A 60% by weight solution was obtained.
Then, it cools to 50 degreeC, 4.1 mass part and 25 mass parts of 25% ammonia aqueous solution are added, methyl ethyl ketone is removed under the temperature of 40 to 60 degreeC under pressure reduction, 710 mass parts of water is added, and a density | concentration is added. By performing the adjustment, a resin composition (PUD-3) having a nonvolatile content of 23% by mass in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 4)
In a reaction vessel, 50 parts by mass of the aliphatic polyester polyol (PES-1) obtained in Synthesis Example 1 and 50 parts by mass of the aromatic polyester polyol (PES-2) obtained in Synthesis Example 2 in a reaction vessel were added at 100 ° C. under reduced pressure. And then cooled to 80 ° C., 94.1 parts by mass of methyl ethyl ketone was added, and the mixture was stirred and mixed uniformly. Next, 8.8 parts by mass of 2,2-dimethylolpropionic acid and 4.2 parts by mass of 1,4-butanediol were added, and then 28.1 parts by mass of tolylene diisocyanate and 0.08 parts by mass of dibutyltin dilaurate were added. In addition, the reaction was carried out at 80 ° C. for 12 hours to carry out the urethanization step. It was confirmed that the isocyanate value was 0.1% or less, 0.4 parts by weight of normal butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the nonvolatile content of the urethane resin having a hydrophilic group A 60% by weight solution was obtained.
Then, it is cooled to 50 ° C., 6.7 parts by mass of triethylamine and 710 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition (PUD-4) having a nonvolatile content of 23% by mass in which the urethane resin was dispersed in an aqueous medium was obtained.

芳香族環式濃度（モル／ｋｇ）：合成したＰＵＤ−１〜ＰＵＤ−４に含まれる芳香族環式濃度である。

Aromatic cyclic concentration (mol / kg): Aromatic cyclic concentration contained in synthesized PUD-1 to PUD-4.

(Production Example 5)
1000 parts by mass of the aromatic polyether ester polyol (PES-4) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and then cooled to 80 ° C., and then 900 parts by mass of methyl ethyl ketone was added and sufficiently stirred. Then, 80 parts by mass of 2,2′-dimethylolpropionic acid and 5 parts of neopentyl glycol were added, and then 284 parts by mass of hexamethylene diisocyanate was added and reacted at 75 ° C. for 8 hours. Subsequently, after cooling to 50 degreeC and adding 61 mass parts of triethylamine and neutralizing, 7,000 mass parts of water was added and water-solubilized. After removing methyl ethyl ketone from the obtained transparent reaction product under reduced pressure at 40 ° C. to 60 ° C., water was added to adjust the concentration, whereby a stable aqueous urethane resin composition having a nonvolatile content of 20% by mass ( PUD-5) was obtained.

(Production Example 6)
Instead of the polyether ester polyol PES-4, a polyether ester polyol PES-5 is used, and the amount of hexamethylene diisocyanate used is changed to 262 parts by mass. A stable aqueous urethane resin composition (PUD-6) having a nonvolatile content of 20% by mass was obtained.

(Production Example 7)
Instead of the polyether ester polyol PES-4, a polyether ester polyol PES-6 is used, and the amount of hexamethylene diisocyanate used is changed to 276 parts by mass. A stable aqueous urethane resin composition (PUD-7) having a nonvolatile content of 20% by mass was obtained.

(Production Example 8)
Instead of the polyether ester polyol PES-4, 400 parts by mass of the polyether ester polyol PES-7 and 600 parts by mass of the polyester polyol PES-5 were used, and the amount of hexamethylene diisocyanate used was changed to 237 parts by mass. A stable aqueous urethane resin composition (PUD-8) having a nonvolatile content of 20% by mass was obtained in the same manner as in Production Example 5 except that this was done.

(Production Example 9)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 1000 parts by mass of polyoxytetramethylene glycol (weight average molecular weight: 2,000), 2.2′-di After adding 78.7 parts by mass of methylolpropionic acid and 884.3 parts by mass of ethyl acetate and mixing uniformly, 237.7 parts by mass of hexamethylene diisocyanate was added, then 0.1 part by mass of dibutyltin dilaurate was added, and For about 4 hours to obtain an ethyl acetate solution.
Subsequently, the ethyl acetate solution of the urethane prepolymer obtained by the above method was cooled to 40 ° C., 68.3 parts by mass of triethylamine was added to neutralize the carboxyl group in the urethane prepolymer, and then ion-exchanged water 2849. Next, 1 part by mass was added, and then 18.4 parts by mass of 80% by mass hydrated hydrazine (hydrazine monohydrate, 80% by mass with respect to the total hydrazine) was added and reacted.
After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and ion-exchanged water was added so that the non-volatile content was 35% by mass to obtain a composition (I).

芳香族環式濃度（モル／ｋｇ）：合成したＰＵＤ−５〜ＰＵＤ−９に含まれる芳香族環式濃度である。

Aromatic cyclic concentration (mol / kg): Aromatic cyclic concentration contained in synthesized PUD-5 to PUD-9.

<Creation of pigment paste>
Styrene-maleic acid half ester (product name “DSS-25” manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 116 mg KOH / g, weight average molecular weight: 42,000, SP: 11.0) 15 parts, hydroxylated 1.57 parts of potassium (an amount corresponding to 0.90 equivalent to the total amount of acidic groups in the styrene-maleic acid half ester) and 83.43 parts of water are mixed and stirred at 70 ° C. using a stirrer. As a result, a translucent resin dispersion was obtained. 40 parts of the resin dispersion, 20 parts of copper phthalocyanine pigment (product name FASTOGEN BLUE 5327 WET manufactured by DIC) and 40 parts of water are mixed and stirred, and 500 parts of 0.3 mmφ ceramic beads are added to this mixture. After that, it was ground for 6 hours with a 6-cylinder sand grinder. After grinding, the ceramic beads were separated to obtain a mill base. The mill base obtained above was mixed and stirred, and subdivided for 3 hours using an ultrasonic homogenizer at an output of 600 W to obtain a pigment paste.

<Examples Preparation of printing agent>
Add 20 parts of the pigment paste, solvent (water, water-soluble solvent, oil-soluble solvent, etc.), 17.4 parts of PUD-1 as urethane resin, and 0.5 part (or 10 parts) of urea (or hydroxyethylurea). Thus, the printing agent of the example was obtained. The composition of each printing agent is shown in the attached table. At the time of addition in each example, the mixture was sufficiently stirred with a dispersion stirrer (TK Homo Disper L manufactured by Tokushu Kika Kogyo Co.).

<Comparative Example Preparation of printing agent>
20 parts of the pigment paste, solvent (water, water-soluble solvent, oil-soluble solvent, etc.), 17.4 parts of PUD-5 as urethane resin, 0.5 part (or 5 parts) of urea (or hydroxyethylurea) are added Thus, the printing agent of the example was obtained. The composition of each printing agent is shown in the attached table. At the time of addition in each example, the mixture was sufficiently stirred with a dispersion stirrer (TK Homo Disper L manufactured by Tokushu Kika Kogyo Co.).

<Evaluation of re-solubility>
30 μL of the obtained printing agents of Examples and Comparative Examples were applied on a slide glass and allowed to stand at 50 ° C. for 10 minutes at an experimental room temperature to prepare a test plate. Thereafter, it was immersed in water at room temperature for 60 seconds, and it was visually confirmed whether it was dissolved again. After immersing for 30 seconds, after removing the colored components on the slide glass and no undissolved particulate matter in the immersion liquid, “◎”, some undissolved residue in the slide glass or immersion liquid. What was confirmed was determined to be “◯”, those having clearly undissolved substances in the slide glass or the immersion liquid, “Δ”, and those having remarkably undissolved substances in the slide glass or the immersion liquid were determined to be “X”. In addition, the printing agent which can be determined as “good” in this experiment exhibits re-solubility by the screen recording method, or can be easily ejected by a cleaning operation after a long pause of printing in the ink jet recording method.

<Evaluation of storage stability>
20 ml of the printing agent obtained in Examples and Comparative Examples was sealed in a glass container and allowed to stand at 50 ° C. for 4 weeks, and then evaluated as follows.
A: Change rate from initial viscosity ± 10% or less B: Change rate from initial viscosity ± 10 to less than 15% C: Change rate from initial viscosity ± 15% or more

  Tables 5 to 8 show the compositions of the printing agents of Examples and Comparative Examples and various evaluation results. The unit of blending in the table is part.

From the results of Tables 5 to 8, the printing resin using the urethane resin (A) having a polyester structure and the wetting agent of the present invention (Examples) was good in storage stability and re-dissolution property. On the other hand, Comparative Examples 1 and 2 using a urethane resin having no polyester structure were both poor.

Claims (7)

A pigment, a pigment dispersant, a water-soluble solvent and / or water, a polyol (a1) added with 1 to 20 moles of alkylene oxide per molecule of a bisphenol compound, and an aromatic polycarboxylic acid A polyester polyol (a1-1) as a reactant, a polyol having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group, and a polyisocyanate (a2) A printing agent, comprising: a urethane resin binder obtained by reacting the above and at least one wetting agent selected from the group consisting of urea, a urea derivative, a pyrrolidone derivative, an alkylglycine, and a saccharide. The printing agent according to claim 1, wherein the alkylene oxide is ethylene oxide. The printing agent according to claim 1 or 2, wherein the pigment dispersant is a styrene-maleic acid copolymer. The printing agent according to any one of claims 1 to 3, wherein the aromatic cyclic concentration contained in the total amount of the polyester polyol (a1-1) is 3 mol / kg or more. The fabric thing which printed the textile printing agent in any one of Claims 1-4 on the fabric. A printing method for printing on a fabric the printing agent according to claim 1. The textile printing method according to claim 6, wherein printing is performed by an ink jet printing method or a screen printing method.