WO2018207636A1 - Textile printing agent, textile printing agent for inkjet recording, printed matter, and manufacturing method - Google Patents

Abstract

The present invention addresses the problem of providing a textile printing agent which exhibits high ink ejection stability even during high-speed or continuous printing operation, and which therefore makes it possible to suppress an increase in printing defect over time, and to make a significant improvement in printed matter production efficiency. The present invention relates to a textile printing agent characterized in that: a dynamic surface tension measured by a maximum bubble pressure method in a surface lifetime of 20 milliseconds is not less than 38 mN/m and not more than 60 mN/m; and a static surface tension measured by a Wilhelmy method is not less than 32 mN/m and not more than 42 mN/m.

Description

PRINTING AGENT, INKJET RECORDING PRINTING AGENT, PRINTED MATERIAL AND PRODUCTION METHOD

The present invention relates to a printing agent that can be used for printing on a fabric, for example.

It is known that a printing agent can be used when printing images such as characters, pictures and designs on fabrics such as woven fabrics, nonwoven fabrics and knitted fabrics.

As the textile printing agent, in general, an aqueous pigment dispersion containing a pigment at a high concentration is diluted with water as necessary, and is obtained by mixing a binder resin and other additives. For example, a textile printing ink for ink-jet recording which is used for printing on a fabric using a polyurethane resin as a binder resin is known (for example, see Patent Document 1).

On the other hand, as described above, a method using an ink jet recording apparatus is known as a method for printing the printing agent on a recording medium. The printing method using an inkjet recording device does not require plate making for each picture or design to be printed, and has advantages such as cost reduction and shortened delivery time in small lot printing, so printing is performed at high speed and continuously. As a possible printing method, application in a wide range of technical fields is being studied.

However, while the industry demands high-definition printed materials having a resolution of about 300 dpi or higher, the above-mentioned high-clear printed materials will be obtained using a conventional textile printing agent and an ink jet recording apparatus. In this case, the ejection direction of the ink ejected from the ink jet head becomes unstable, which may cause problems such as printing defects. In particular, when a head having a drive frequency of 20 kHz or more is used as an ink jet head provided in the ink jet recording apparatus, the ejection direction of the ink ejected from the ink jet head becomes extremely unstable, causing problems such as poor printing of printed matter. There were cases where it was easy to cause.

JP 2016-199643 A

The problem to be solved by the present invention is that it is excellent in ink ejection stability even in printing scenes performed at high speed or continuously, so that it is possible to suppress an increase in printing defects over time, and as a result, the production efficiency of printed matter It is to provide a printing agent capable of drastically improving the quality.

The present invention has a dynamic surface tension of 38 mN / m or more and 60 mN / m or less at a surface lifetime of 20 milliseconds measured by the maximum bubble pressure method, and a static surface tension measured by the Wilhelmy method of 32 mN / m or more and 42 mN. The present invention relates to a printing agent characterized by being / m or less.

The textile printing agent of the present invention is excellent in ink ejection stability even at high-speed or continuous printing scenes, and therefore can suppress an increase in printing defects over time, resulting in production of printed matter. The efficiency can be dramatically improved.

It is a schematic diagram of the microreactor used by this invention.

The printing agent of the present invention has a dynamic surface tension of 38 mN / m or more and 60 mN / m or less at a surface life of 20 milliseconds measured by the maximum bubble pressure method, and a static surface tension measured by the Wilhelmy method of 32 mN / m. m or more and 42 mN / m or less.

The printing agent having the dynamic surface tension of 38 mN / m or more and 60 mN / m or less is appropriately supplied with ink to the nozzle through the ink flow path in the vicinity of the piezo element regardless of the vibration of the piezo element of the inkjet head. The In addition, since the textile printing agent has sufficient liquid repellency with respect to the nozzle surface of the ink jet head, the air / liquid interface (interface between air and ink) is not easily destroyed by vibration caused by driving the ink jet head or the like. As a result, even in a scene where the driving frequency is gradually high and the printing speed is high, high-resolution printed matter with a resolution of 300 dpi or more can be efficiently produced without causing an abnormality in the ink ejection direction. Can be produced well.

The printing agent of the present invention has a dynamic surface tension at a surface life of 20 msec within the above range, and a dynamic surface tension at a surface life of 1000 msec measured by the maximum bubble pressure method is from 33 mN / m to 48 mN / m. Using a material having a diameter of m or less can form a gas-liquid interface that is not easily destroyed by vibration or the like. As a result, even if the drive frequency is gradually high and the printing speed is high, It is preferable because excellent discharge stability can be maintained.

The difference between the dynamic surface tension at the surface lifetime of 20 milliseconds and the dynamic surface tension at the surface lifetime of 1000 milliseconds is preferably less than 15 mN / m, more preferably 4 mN / m or more and less than 15 mN / m, 4 mN / m or more and less than 13 mN / m, the wettability of the printing agent with respect to the ink flow path of the inkjet head is quickly stabilized, and the ink is excellent even when inkjet printing is performed at high speed or continuously. In particular, it is preferable because the discharge stability can be maintained.

The dynamic surface tension is a value measured at a surface life of 20 msec and 1000 msec using a maximum bubble pressure method in an environment at a temperature of 25 ° C. and measured from a surface life of 20 msec to 2000 msec.

On the other hand, as the printing agent of the present invention, one having not only a dynamic surface tension within the above range but also a static surface tension measured by the Wilhelmy method of 32 mN / m or more and 42 mN / m or less is used. This is necessary for achieving the effects of the present invention. A printing agent having a static surface tension of less than 32 mN / m or more than 42 mN / m may be excessively wetted with respect to the ink flow path of the ink jet head or may not have sufficient wettability. When the formation of the liquid interface is hindered and ink jet printing is performed at high speed or continuously, there may be a problem that impairs the excellent ejection stability of the ink. Similarly, the printing agent having a static surface tension of less than 32 mN / m does not have sufficient liquid repellency with respect to the nozzle surface of the ink jet head, and is generated at the time of ejection in a continuous ejection scene. Ink mist tends to adhere to the nozzle surface, which may cause an abnormality in the ink ejection direction.

By using a printing agent having a dynamic surface tension and a static surface tension within the above range, even when ink jet printing is performed at high speed or continuously, the excellent ejection stability of the ink can be maintained. The increase in printing defects over time can be suppressed, and the production efficiency of printed matter can be dramatically improved.

The static surface tension is preferably 32 mN / m or more and 40 mN / m or less in order to further improve the above effect. In addition, the said static surface tension points out the value measured by the Wilhelmy method in the environment of temperature 25 degreeC.

As a method for adjusting the surface tension of the printing agent, it is preferable to use a surfactant.

For example, a nonionic surfactant is preferably used as the surfactant.

Examples of the nonionic surfactant include acetylene glycol surfactants, acetylene alcohol surfactants, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkylallyl. Ethers such as 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 Use ester surfactants such as lenmonooleate and polyoxyethylene stearate, silicon surfactants such as dimethylpolysiloxane, and fluorine-containing surfactants such as fluorine alkyl esters and perfluoroalkyl carboxylates. Can do.

Among these, the use of an acetylene glycol surfactant or a silicone surfactant as the nonionic surfactant is such that the dynamic surface tension and static surface tension of the printing agent are within the above-described ranges. As a result, even when ink jet printing is performed at high speed or continuously, excellent discharge stability of ink can be maintained, so that increase in printing defects over time can be suppressed. It is preferable because a printing agent that can dramatically improve the production efficiency of printed matter can be obtained.

Examples of the acetylene glycol surfactants include Surfynol 61, 82, 104, 420, 440, 465, 485, 2502, Dinol 604, 607, Olfin E1004, E1006 from Nissin Chemical Industry Co., Ltd. , E1010 and the like.

Examples of the silicone surfactant include Silface SAG503A and SAG014 manufactured by Nissin Chemical Industry Co., Ltd., TEGOWETKL245, 250, 260, 270, and 280 manufactured by Evonik.

The surfactant is preferably used in the range of 0.1% by mass to 2.5% by mass with respect to the total amount of the printing agent, and in the range of 0.1% by mass to 1.5% by mass. Even when inkjet printing is performed at high speed or continuously, excellent ink ejection stability can be maintained, so that the increase in printing defects over time can be suppressed, and the production efficiency of printed matter has jumped. It is preferable because a printing agent that can be improved in terms of quality can be obtained.

As the printing agent of the present invention, one containing a binder resin can be used.

As the binder resin, a resin that can be dispersed in a solvent such as water or a water-soluble resin that can be dissolved in a solvent such as water can be used.

The binder resin is for fixing the pigment on the fabric. In the case of printing on a fabric, if an ink having a high content of the binder resin is used, fastness such as washing fastness, dry friction fastness and wet friction fastness of the printed matter is improved, but the texture of the fabric is slightly hardened. There is a tendency. Therefore, the binder resin is preferably used in a range of 20% by mass or less, more preferably in a range of 10% by mass or less, and the lower limit is 1% by mass or more with respect to the total mass of the printing agent. Preferably, 3% by mass or more is more preferable for obtaining a printed matter excellent in fastness.

The binder resin is for fixing the pigment on the recording medium as described above. In particular, in the case of printing on a fabric, if a glass transition temperature exceeding room temperature is used, the texture of the fabric tends to become slightly hard. Therefore, the binder resin having a glass transition temperature of 0 ° C. or less is particularly preferable for maintaining good fastness and texture even when a printing agent or printed matter is used in a low temperature region. preferable.

The ratio of the binder resin to the pigment is usually within the range used for the printing agent. For example, the ratio of the binder resin to the pigment is preferably 1: 3 to 8: 1, and preferably 1: 2 to The range of 3.5: 1 is more preferable in order to obtain a printed matter having much more excellent fastness.

As the binder resin, it is preferable to use a binder having a large weight average molecular weight, and a binder resin having a weight average molecular weight of 200,000 or less may be used in order to obtain a printed matter having further excellent fastness. This is preferable in order to obtain a printed matter having much more excellent fastness and to suppress the increase in the viscosity of the ink.

Examples of the binder resin include urethane resins, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, potassium acrylate-acrylonitrile copolymers, vinyl acetate-acrylic ester copolymers, Acrylic copolymers such as acrylic acid-alkyl acrylate copolymer; styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, styrene-α- Styrene-acrylic acid resins such as methylstyrene-acrylic acid copolymer and styrene-α-methylstyrene-acrylic acid-alkyl acrylate copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene-acrylic acid Both Polymer; vinyl naphthalene-maleic acid copolymer; vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, acetic acid Vinyl acetate copolymers such as vinyl-acrylic acid copolymers and salts thereof can be used.

Among them, it is preferable to use a urethane resin or an acrylic resin as the binder resin because it is easily available and improves the fastness of the printed matter, and particularly the fastness to washing of the printed matter on the fabric and the fastness to dry friction. And preferred for further improving wet fastness to friction.

Examples of the urethane resin include one or more polyols selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol, and an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group. A urethane resin obtained by reacting a polyol having a certain hydrophilic group with polyisocyanate is used.

The weight average molecular weight of the urethane resin is preferably 5000 to 200000, more preferably 20000 to 150,000, in order to further improve the fastness of the printed matter.

Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neo Pentyl glycol, glycerin, trimethylol ethane, trimethylol propane, sorbitol, sucrose, aconite sugar, femellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2, Compounds having two or more active hydrogen groups such as 3-propanetrithiol are added to ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohi Phosphorus, tetrahydrofuran, obtained by addition polymerization of cyclic ether compounds such as cycloalkyl Fe xylene, or the cyclic ether compound cationic catalyst, protonic acids include those of Lewis acid to ring-opening polymerization as a catalyst.

The polyester polyol is obtained by dehydration condensation reaction of diol compound, dicarboxylic acid, hydroxycarboxylic acid compound, etc., ring-opening polymerization reaction of cyclic ester compound such as ε-caprolactone, and copolymerization of polyester obtained by these reactions. It is done. Examples of the diol compound used as a raw material for the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof.

Examples of the dicarboxylic acid used as the raw material for the polyester polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4. -Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (Phenoxy) ethane-p, p′-dicarboxylic acid and the like.

Examples of the hydroxycarboxylic acid used as a raw material for the polyester polyol include p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid.

As the polycarbonate polyol, for example, those obtained by reacting a carbonate with a low molecular weight polyol, preferably a linear aliphatic diol, can be used.

As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.

Examples of the low molecular weight polyol that can react with the carbonic acid ester include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, and 1,3-butane. Diol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , Hydroquinone, resorcin, bisph Relatively low molecular weight dihydroxy compounds such as Nord-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexa Polyester polyols such as methylene succinate and polycaprolactone can be used.

The polycarbonate structure is preferably used in the range of 10% by mass to 90% by mass with respect to the total mass of the polyol and the polyisocyanate used for the production of the polycarbonate urethane resin.

Further, the urethane resin has a hydrophilic group for imparting dispersion stability in the printing agent.

As the hydrophilic group, those generally referred to as an anionic group, a cationic group, and a nonionic group can be used, and among them, an anionic group or a cationic group is preferably used.

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, Examples thereof include metal base compounds containing K, Li, Ca, etc. Among them, it is preferable to select an organic amine having a boiling point of 100 ° C. or less from the viewpoint of reducing the residue on the dry film.

In addition, as the cationic group, for example, a tertiary amino group can be used. 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.

Examples of the nonionic group include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and 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.

When the hydrophilic group is present in an amount of 0.5 to 30% by mass relative to the entire urethane resin, the water-dispersibility is further improved, and the range is from 1 to 20% by mass. More preferred.

Further, the printing agent of the present invention can use a crosslinking agent described later for the purpose of further improving fastness. When using the said crosslinking agent, it is preferable to use what has a functional group which can carry out a crosslinking reaction with the functional group which the said crosslinking agent has as said urethane resin.

Examples of the functional group 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 in the aqueous medium, and when they undergo a crosslinking reaction, they also act as the functional group and can partially undergo a crosslinking reaction of the crosslinking agent.

When a carboxyl group or the like is used as the functional group, the urethane resin preferably has an acid value of 2 to 55, and a resin having an acid value of 15 to 50 can be used for fastness. It is preferable when improving. In addition, the acid value as used in the field of 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.

The urethane resin can be produced, for example, by reacting a polyol, a polyisocyanate, and, if necessary, a chain extender.

As the chain extender, polyamines and other active hydrogen atom-containing compounds can be used.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 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; disuccinate Dorazide, 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 compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl. Glycols such as glycol, saccharose, methylene glycol, glycerin, sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc. Phenols and water can be used

For example, the chain extender has an equivalent of an amino group and an active hydrogen atom-containing group of the chain extender to an equivalent of an isocyanate group of a urethane prepolymer obtained by reacting the polyol and polyisocyanate. It is preferably used in the range of 1.9 or less (equivalent ratio), more preferably in the range of 0.0 to 1.0 (equivalent ratio), more preferably 0.5 (equivalent ratio). Is preferred

The chain extender can be used when the polyol and polyisocyanate are reacted or after the reaction. Moreover, when the urethane resin obtained above is dispersed in an aqueous medium to make it water-based, the chain extender can be used.

Examples of polyols other than those described above include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, , 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol Bisphenol A, hydrogenated bisphenol A, hydroquinone and their alkylene oxide adducts, glycerin, trimethylolethane, trimethylolpropane, sorbitol, Relatively low molecular weight polyol of pentaerythritol, and the like. These polyols can be used alone or in combination of two or more.

Examples of the polyisocyanate that reacts with the polyol to form a urethane resin include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate can be used alone or in combination of two or more.

The acrylic resin that can be used as the binder resin is not particularly limited, and examples thereof include homopolymerization or copolymerization of (meth) acrylate, and a resin obtained by copolymerization with a vinyl monomer that can be copolymerized with (meth) acrylate. . In the present invention, “(meth) acrylic acid” refers to methacrylic acid or acrylic acid, “(meth) acrylate” refers to methacrylate or acrylate, and “(meth) acryloyl” refers to methacryloyl or acryloyl. Point to.

Examples of vinyl monomers copolymerizable with (meth) acrylate and (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t -Alkyl (meth) acrylates such as butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing monomers such as 2-hydroxypropyl (meth) acrylate; alkyl polyalkylene glycol mono (meso) such as methoxypolyethylene glycol mono (meth) acrylate and methoxypolypropylene glycol mono (meth) acrylate ) Acrylate; fluorine-based (meth) acrylates such as perfluoroalkylethyl (meth) acrylate; styrene, styrene derivatives (p-dimethylsilylstyrene, (p-vinylphenyl) methyl sulfide, p-hexynylstyrene, p-methoxystyrene) , P-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, etc.), vinyl naphthalene, vinyl anthracene, 1,1-diphenylethylene, etc. Vinyl compounds; glycidyl (meth) acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Methylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) ) Phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate, urethane (meth) acrylate and other (meth) acrylate compounds; dimethylaminoethyl (meth) acrylate (Meth) acrylates having an alkylamino group such as diethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate; vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine and naphthylvinylpyridine; Conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene, etc. Is mentioned. These monomers can be used alone or in combination of two or more.

For the acrylic resin used in the present invention, it is preferable to use a resin obtained by copolymerizing a monomer having a specific functional group in addition to the above-mentioned monomers in order to improve the texture of the printed matter. Examples of such a monomer having a functional group include a monomer having a carboxyl group, a monomer having an epoxy group, a monomer having a hydrolyzable silyl group, and a monomer having an amide group.

As the monomer having a carboxyl group, for example, (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, citraconic acid and the like can be used.

Examples of the monomer having a hydrolyzable silyl group include vinylsilane compounds such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy) silane; 3- (meth) acryloyloxypropyltri (Meth) acryloyloxyalkylsilane compounds such as methoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, etc. Can be used. These monomers can be used alone or in combination of two or more.

As the monomer having an amide group, acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, diacetone acrylamide, and the like can be used.

The dispersion form of the acrylic resin in water is not particularly limited, and examples thereof include an emulsion forcibly emulsified with an emulsifier, a dispersion having a nonionic group or a neutralized ionic group in the resin, and the like. In particular, the acrylic resin is preferably a dispersion obtained by neutralizing an acrylic resin having a carboxyl group with a basic compound. The said basic compound can use the same thing as the basic compound illustrated as what can be used for neutralization of the carboxyl group etc. which the said urethane resin has.

As the printing agent of the present invention, one containing a colorant can be used. As the colorant, for example, a pigment or a dye can be used, and a pigment is preferably used. As the pigment, for example, an inorganic pigment or an organic pigment can be used.

As the inorganic pigment, for example, carbon black produced by a known method such as titanium oxide, iron oxide, contact method, furnace method, thermal method, or the like can be used.

Examples of the organic pigment 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 No. manufactured by Mitsubishi Chemical Corporation as long as the pigment is used in black ink. 2300, no. 2200B, no. 900, no. 980, no. 960, no. 33, no. 40, no. 45, no. 45L, no. 52, HCF88, MCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. made by Columbia, Regal 400R, Regal 330R, Regul 660R, Regul 660R, made by Cabot 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are Color Black FW1, FW2, FW2V, FW18, FW200, 170, S150, S35, P U, V, 1400U, Sp cial Black 6, Special Black 5, Special Black 4, it is possible to use the same 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180 such as carbon black.

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 violet 19, 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 and their pigments And a mixture or solid solution of at least two pigments selected from the group consisting of:

Specific examples of pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 63, 66, and the like.

Specific examples of pigments used in red ink include C.I. I. CI Pigment Red 17, 49: 2, 112, 149, 150, 177, 178, 179, 188, 254, 255, and 264 are preferably used.

Specific examples of pigments used in orange ink include C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, 71, 73, 81, and the like.

* Specific examples of pigments used in green ink include C.I. I. Pigment green 7, 10, 36, 58, 59, and the like.

Specific examples of pigments used in violet ink include C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

As the pigment, the above-mentioned pigments can be used alone or in combination of two or more.

As the pigment, for example, dry powder and wet cake can be used.

As the pigment, a pigment having a particle diameter of 25 μm or less is preferable, and a pigment having a particle diameter of 1 μm or less is particularly preferable. When the particle diameter is within this range, the pigment does not easily settle in the textile and the pigment dispersibility is good.

For the measurement of the particle diameter, for example, a value measured using a transmission electron microscope (TEM) was adopted.

As the pigment, a so-called self-dispersing pigment having a water-dispersibility imparting group such as a hydroxyl group or a carboxyl group on the surface of the pigment, or a resin-dispersed pigment in which the surface of the pigment is coated with a dispersing resin may be used. it can.

The dispersion resin can be suitably used when the pigment is stably dispersed in water. As the ratio of the dispersion resin and the pigment, for example, when the resin dispersion type pigment is used, the mass ratio is preferably 1: 100 to 1: 1, and 1:10 to 1: A range of 1 is more preferred.

The dispersion resin and the binder resin are preferably used in a range where their mass ratio [dispersion resin / binder] is 0.02 to 2, and used in a range of 0.06 to 1. This is particularly preferable for obtaining an ink having further excellent fastness and excellent ink ejection stability.

Examples of the dispersion resin include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins having an anionic group such as acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene. -Styrene-acrylic compounds having an anionic group such as methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer Examples thereof include resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and urethane resins having an anionic group. These may form a salt.

Among these, a dispersion resin having an anionic group such as a carboxyl group is preferable because of excellent dispersion stability, and a dispersion resin having an anionic group and an aromatic group such as styrene is preferable. Specific examples of such a dispersion resin having an anionic group and an aromatic group include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- α-Methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid And a copolymer.

The weight average molecular weight of the dispersion resin is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, in order to maintain a stable dispersion state of the pigment.

As the printing agent of the present invention, those containing a solvent such as water can be used.

As the water, for example, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water can be used. As the water, it is possible to effectively prevent generation of mold and bacteria in the printing agent of the present invention by using water irradiated with ultraviolet rays, water sterilized with hydrogen peroxide or the like. preferable.

As the solvent, an organic solvent may be used together with water. As the organic solvent, any of those used for printing agents can be used. Organic solvents are broadly classified into those that function as humectants and those that function as penetrating solvents.

Examples of the organic solvent that can be used as the humectant include glycerin, ethylene glycol adducts of glycerin (specific examples: liponic EG-1 (manufactured by Lipochemical)), diglycerin, polyglycerin, ethylene glycol, propylene glycol. 1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol (specific examples: “# 200”, “# 300”, “# 400”, “# 4000”, “# 6000” manufactured by Wako Pure Chemical Industries, Ltd.) 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, thiodiglycol, sulfolane, dimethyl sulfoxide, neopentyl alcohol, trimethylolpropane, 2,2-dimethylpropanol and the like. These organic solvents can be used alone or in combination of two or more.

Examples of the organic solvent that can be used as the penetrating solvent include monohydric or polyhydric alcohols, amides, ketones, keto alcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, and polyalkylene glycols. Propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol Polyols such as 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol Polyhydric alcohol alkyl ethers such as methyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and propylene glycol monobutyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, and polyhydric acids Alcohol aralkyl ethers, lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, ε-caprolactam, 1,3-dimethylimidazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, glycerin Polyoxyalkylene adduct, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolane, propylene glycol monomethyl ether acetate , Dimethyl sulfoxide, diacetone alcohol, dimethyl formamide, propylene glycol monomethyl ether and the like. These organic solvents can be used alone or in combination of two or more.

(Printing agent manufacturing method)
The textile printing agent of the present invention produces an aqueous pigment dispersion containing the pigment in a high concentration, and the aqueous pigment dispersion, water, a surfactant, and, if necessary, the binder resin and other additives. And can be produced by mixing.

Examples of the method for producing the aqueous pigment dispersion include the following methods (1) to (3).
(1) A method of preparing an aqueous pigment dispersion by adding a pigment to an aqueous medium containing a dispersion resin and water, and then dispersing the pigment in an aqueous medium such as water using a stirrer or a dispersing device. .
(2) The pigment and the dispersion resin are kneaded using a kneader such as two rolls or a mixer, and the obtained kneaded product is added to an aqueous medium containing water, and the mixture is aqueous using a stirrer or a dispersing device. A method for preparing a pigment dispersion.
(3) After adding the pigment to the solution obtained by dissolving the dispersion resin in an organic solvent compatible with water, such as methyl ethyl ketone and tetrahydrofuran, the pigment is added to the organic solvent using a stirrer or a dispersing device. And then phase-emulsifying using an aqueous medium, and then distilling off the organic solvent to prepare an aqueous pigment dispersion.

The kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, an intensive mixer, and a planetary mixer.

Further, the stirring device or the dispersion 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. . As the stirring device or the dispersing device, the one device may be used alone, or two or more devices may be used in combination.

The amount of the pigment relative to the entire aqueous pigment dispersion is preferably 5% by mass to 60% by mass in order to further improve the dispersion stability, and more preferably 10% by mass to 50% by mass.

In addition, after the aqueous pigment dispersion is produced, it may be subjected to an impurity removal step by ion exchange treatment or ultra-treatment, 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.

Further, as the textile printing agent, it is preferable to remove coarse particles by centrifugal separation or filtration treatment before and after the production of the textile printing agent in order to maintain good image characteristics of the printed matter.

The above-mentioned printing agent has a pigment concentration of 1% by mass to 20% by mass in order to ensure the necessity of obtaining a sufficient image density and to further improve the dispersion stability of the pigment in the printing agent. Is preferred. In addition, when preparing the pigment concentration with the additive or the like in this way, the additive contains the binder resin in order to prevent a decrease in dispersion stability due to direct contact between the aqueous pigment dispersion and the additive or the like. It is preferable to add together.

As the textile printing agent, additives containing antiseptics, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents and the like can be used.

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 carboxymethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, 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 the antioxidant or ultraviolet absorber 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 additive can be supplied, for example, when the aqueous pigment dispersion, a binder resin, a solvent, and the like are mixed to produce a printing agent.

Further, as the printing agent of the present invention, one containing a water-soluble organic solvent can be used in order to obtain a printing agent excellent in moisture retention and permeation adjustment to a recording medium.

Examples of the water-soluble organic solvent include mono- or polyhydric alcohols, amides, ketones, keto alcohols, cyclic ethers, glycols, lower alkyl ethers of polyhydric alcohols, polyalkylene glycols, Glycerin, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 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-pentane Diol, 1,2,6- Polyols such as xanthriol, 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 glycol mono Polyhydric alcohol alkyl ethers such as butyl 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 -Lactams such as caprolactam, 1,3-dimethylimidazo Lidinone 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, diacetone Alcohol, dimethylformamide, propylene glycol monomethyl ether and the like can be used alone or in combination of two or more.

As the water-soluble organic solvent, saccharides can also be used. Examples of the saccharide 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 printing agent of the present invention can be suitably used exclusively as an ink for ink jet recording. The ink-jet ink can be widely used from a small home printer to a large industrial printer. In addition, any ink jet heads for low viscosity to high viscosity can be used.

The fabric that can be 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, rayon, or a mixed cloth of these can be used. The fabric used in the present invention may be in the form of a roll and can be printed at a maximum width of 2 m and about 20 m / hour. In addition, the fabric can be printed on a fabric substrate that has been subjected to a pretreatment having a printing agent receiving layer.

Hereinafter, the effects of the present invention will be described in detail using examples and comparative examples.

<Synthesis Example of Dispersing Resin (P-1)>
A hexane solution of BuLi and a styrene solution in which styrene was previously dissolved in tetrahydrofuran were introduced into the T-shaped micromixer M1 from the tube reactors P1 and P2 shown in FIG.

Next, the polymer obtained in the above step is moved to the T-shaped micromixer M2 through the tube reactor R1 shown in FIG. 1, and the growth regulator of the polymer introduced from the tube reactor P3 (α− Trapped with methylstyrene (α-MeSt)).

Next, a tert-butyl methacrylate solution in which tert-butyl methacrylate is previously dissolved in tetrahydrofuran is introduced into the T-shaped micromixer M3 from the tube reactor P4 shown in FIG. 1, and the trapped polymer moved through the tube reactor R2 and A continuous living anion polymerization reaction was performed. Thereafter, the block copolymer (PA-1) composition was prepared by quenching the living anionic polymerization reaction by supplying methanol.

When the block copolymer (PA-1) composition was produced, the reaction temperature was set to 24 ° C. by burying the entire microreactor shown in FIG.

The molar ratio of monomers constituting the block copolymer (PA-1) obtained by the above method is as follows:
(BuLi / styrene / α-methylstyrene / tert-butyl methacrylate) = 1.0 / 12.0 / 1.3 / 8.1.

The obtained block copolymer (PA-1) composition was hydrolyzed by treating with a cation exchange resin, then distilled off under reduced pressure, and the resulting solid was pulverized to obtain a weight average molecular weight of 2710. A powdery dispersion resin (P-1) having an acid value of 145 was obtained.

The physical properties of the obtained dispersion resin (P-1) were measured as follows.

(Measurement method of weight average molecular weight (Mw))
It measured by the gel permeation chromatography (GPC) method on the following conditions.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.

"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (THF solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

(Measurement method of acid value)
The measurement was performed according to JIS test method K 0070-1992. It was determined by dissolving 0.5 g of sample in THF and titrating with 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.

<Synthesis Example of Dispersing Resin (P-2)>
In a reaction vessel of an automatic polymerization reaction device (polymerization tester DSL-2AS type, manufactured by Sakai Sangyo Co., Ltd.) having a reaction vessel equipped with a stirring device, a dripping device, a temperature sensor, and a reflux device having a nitrogen introduction device on the top, 1200 parts by mass of isopropyl alcohol was charged, and the inside of the reaction vessel was purged with nitrogen while stirring. After raising the temperature in the reaction vessel to 80 ° C. while maintaining a nitrogen atmosphere, 75.0 parts by mass of 2-hydroxyethyl methacrylate, 260.8 parts by mass of methacrylic acid, 400.0 parts by mass of styrene, methacrylic acid from the dropping device. 234.2 parts by mass of benzyl, 30.0 parts by mass of glycidyl methacrylate and 80.0 parts by mass of “Perbutyl (registered trademark) O” (active ingredient t-butyl peroxy-2-ethylhexanoate, manufactured by NOF Corporation) The mixture was added dropwise over 4 hours. After completion of the dropwise addition, the reaction was further continued at the same temperature for 15 hours, and then a part of isopropyl alcohol was distilled off under reduced pressure, and the solid content ratio was adjusted to 42.5% by mass, whereby the weight average molecular weight 23000, acid A dispersion resin (P-2) containing a styrene- (meth) acrylic acid copolymer having a value of 170 was obtained.

<Production Example 1> Production method of aqueous pigment dispersion (A1) As a pigment, 150 parts by mass of Fastogen Super Magenta RY (manufactured by DIC Corporation, CI Pigment Red 122) and 30 of the dispersion resin (P-1) 150 parts by weight of triethylene glycol and 11.5 parts by weight of 34% by weight potassium hydroxide aqueous solution were charged into a 1.0 L intensive mixer (Nippon Eirich Co., Ltd.), rotor peripheral speed 2.94 m / s, pan The kneading was carried out at a peripheral speed of 1 m / s for 60 minutes.

Next, 450 parts by mass of ion-exchanged water is gradually added to the kneaded product in the intensive mixer container while continuing stirring, and then 208.5 parts by mass of ion-exchanged water is further added and mixed to obtain a pigment concentration of 15. 0% by mass of an aqueous pigment dispersion (A1) was obtained.

<Production Example 2> Production method of aqueous pigment dispersion (A2) Fastogen Super Sagent-RY (manufactured by DIC Corporation, CI Pigment Red 122) 150 parts by mass, Fastogen Blue SBG-SD (manufactured by DIC Corporation) , CI Pigment Blue 15: 3) was used in the same manner as in Production Example 1 to obtain an aqueous pigment dispersion (A2), except that 150 parts by mass of CI Pigment Blue 15: 3) was used.

<Production Example 3> Method for producing aqueous pigment dispersion (A3) Fast Yellow 7413 (manufactured by Sanyo Dye Co., Ltd.) instead of 150 parts by mass of Fastogen Super Magenta RY (DIC Corporation, CI Pigment Red 122), An aqueous pigment dispersion (A3) was obtained in the same manner as in Production Example 1, except that 150 parts by mass of CI Pigment Yellow 74) was used.

<Production Example 4> Production method of aqueous pigment dispersion (A4) Fastogen Super Super Magenta RY (manufactured by DIC Corporation, CI Pigment Red 122) instead of 150 parts by mass # 960 (manufactured by Mitsubishi Chemical Corporation, C An aqueous pigment dispersion (A4) was obtained in the same manner as in Production Example 1, except that 150 parts by mass of I. Pigment Black 7) was used.

<Production Example 5> Production method of aqueous pigment dispersion (B1) In a mixing tank equipped with a cooling jacket, 360 parts by weight of Fastogen Super Magenta RY (manufactured by DIC Corporation, CI Pigment Red 122), and the dispersion 170 parts by mass of resin (P-2), 61 parts by mass of a 25% by mass aqueous sodium hydroxide solution, 180 parts by mass of isopropyl alcohol, and 1220 parts by mass of ion-exchanged water were stirred and mixed with a three-one motor for 1 hour. The obtained mixed liquid is passed through a dispersion apparatus (SC mill SC100 / 32 type, manufactured by Mitsui Mining Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm, and the circulation system (dispersion liquid discharged from the dispersion apparatus is placed in the mixing tank. It was dispersed by the return method). During the dispersion process, the dispersion temperature was controlled to be kept at 30 ° C. or lower by passing cold water through the cooling jacket, and the rotor peripheral speed of the dispersion apparatus was fixed at 11.25 m / second and dispersed for 4 hours. After the dispersion was completed, the dispersion stock solution was extracted from the mixing tank, and then the mixing tank and the dispersion device flow path were washed with 1000 parts by mass of water and mixed with the dispersion stock solution to obtain a mill dispersion.

The mill dispersion was put into a glass distillation apparatus, and the whole amount of isopropyl alcohol and a part of water were distilled off. After allowing to cool to room temperature, 2% by mass hydrochloric acid was added dropwise with stirring to adjust the pH to 3.5, and the solid content was filtered with a Nutsche filter and washed with water to obtain a wet cake.

The wet cake was taken in a container, adjusted to pH 9.0 by adding a 25% by mass aqueous sodium hydroxide solution, and redispersed with a disper (TK Homo Disper 20 type, manufactured by Tokushu Kika Kogyo Co., Ltd.). Thereafter, through a centrifugation step (6000 G, 30 minutes), ion exchange water was further added to obtain an aqueous pigment dispersion (B1) having a solid content of 18% by mass.

<Production Example 6> Synthesis of Urethane Resin (PUD-1) Obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. 500 parts by mass of the obtained polycarbonate polyol (number average molecular weight 2000), 37.7 parts by mass of 2,2-dimethylolpropionic acid and 420 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, 92.4 parts by mass of tolylene diisocyanate was added, 0.1 parts by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-1” (acid) with a weight average molecular weight of 37000 was added. An organic solvent solution having a value of 25) was obtained.

Thereafter, the mixture is cooled to 50 ° C., 29.8 parts by mass of triethylamine and 2069 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 urethane resin (PUD-1) composition having a nonvolatile content of 23% by mass, a weight average molecular weight of 40000, an acid value of 35, and a glass transition temperature of −15 ° C. was obtained by dispersing the urethane resin in an aqueous medium.

The physical properties of the obtained urethane resin (PUD-1) were measured as follows.

(Measurement method of weight average molecular weight (Mw))
It measured on the above-mentioned conditions by the gel permeation chromatography (GPC) method.

(Measurement method of acid value)
It was determined in accordance with JIS test method K 0070-1992 under the above-mentioned conditions.

(Measurement method of glass transition temperature)
The glass transition temperature of the urethane resin (PUD-1) was measured using DSC.

<Example 1> Preparation of printing agent 26.7 parts by mass of the aqueous pigment dispersion (A1), 0.6 part by mass of a surfactant (Surfinol 420), and 26. of the urethane resin (PUD-1) composition. A printing agent (C1) was obtained by mixing 1 part by mass, 20.0 parts by mass of glycerin as a moisturizer, 5.0 parts by mass of triethylene glycol, and ion-exchanged water so that the total mass was 100. 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., Ltd.).

<Examples 2 to 11 and Comparative Examples 1 to 3> Preparation of printing agent In place of 0.6 parts by mass of surfactant (Surfinol 420), the types and addition amounts of surfactants listed in Tables 1 to 3 were used. Printing agents (C2 to C11 and D1 to D3) were obtained in the same manner as in Example 1, except that the changes were made.

<Example 12> Preparation of printing agent Instead of 0.6 parts by mass of surfactant (Surfinol 420), the type and amount of surfactant listed in Table 2 were changed, and the amount of glycerin used was 20 A printing agent (C12) was obtained in the same manner as in Example 1 except that the amount was changed from 0.0 part by mass to 30.0 parts by mass.

<Examples 13 to 15> Preparation of printing agent Aqueous pigment dispersions (A2 to A4) shown in Table 1 were used instead of the aqueous pigment dispersion (A1), and the surfactant (Surfinol 420) was 0.6 mass. Example 1 except that the type and addition amount of the surfactant were changed as shown in Tables 2 and 3 and the amount of glycerin was changed from 20.0 parts by mass to 30.0 parts by mass instead of the parts. Printing agents (C13 to C15) were obtained in the same manner as described above.

<Example 16> Preparation of printing agent In place of the aqueous pigment dispersion (A1), the aqueous pigment dispersion (B1) shown in Table 1 was used, and instead of 0.6 parts by mass of the surfactant (Surfinol 420). A printing agent (C16) was obtained in the same manner as in Example 1 except that the surfactants were changed to the types and addition amounts of the surfactants shown in Table 3.

<Example 17, Comparative Example 4> Preparation of printing agent Instead of 0.6 parts by mass of surfactant (Surfinol 420), the type and amount of surfactants listed in Table 3 were changed, and glycerin A printing agent (C17, D4) was obtained in the same manner as in Example 1 except that the amount used was changed from 20.0 parts by mass to 30.0 parts by mass.

<Evaluation of storage stability>
The viscosity of the printing agent immediately after production by the above method was measured using an E-type viscometer in an environment of 25 ° C.

Next, 20 ml of the printing agent was sealed in a glass container, and the viscosity of the printing agent after standing at 60 ° C. for 4 weeks was measured using an E-type viscometer.

The rate of change of the viscosity of the printing agent after standing was calculated from the viscosity of the printing agent immediately after the production, and was evaluated based on the following criteria.
Rate of change (%) = [{(viscosity of printing agent after standing) − (viscosity of printing agent immediately after production)} / (viscosity of printing agent immediately after production)]
◎: Less than ± 5% ○: ± 5 to less than 10% △: ± 10 to less than 15% ×: ± 15% or more

<Evaluation of continuous discharge performance>
Using a piezo-type inkjet head, purging the printing agent on the head, wiping the nozzle surface of the head, printing a nozzle check pattern on the coated paper at a driving frequency of 10 kHz, and discharging the print pattern Or, the number of discharge deviations was confirmed. Next, after about 150,000 discharges of the printing agent were performed at a driving frequency of 10 kHz, a nozzle check pattern was printed again on the coated paper at a driving frequency of 10 kHz, and the number of ejection omissions and twists in the printing pattern was confirmed. The reason for using coated paper as the recording medium is that the surface of the coated paper is relatively smooth with few irregularities on the surface, and the printing agent is difficult to penetrate into the coated paper. This is because it is possible to accurately determine whether a pattern is missing or twisted.

A value calculated based on the formula [(number of discharge omissions and deviations in the second time) − (number of omissions and deviations in the first time)] was evaluated as “◯”, and 3-5 What was was evaluated as “Δ”, and those that were 6 or more were evaluated as “x”.

<Evaluation of high frequency ejection performance>
Using a piezo-type inkjet head, purging the printing agent on the head, wiping the nozzle surface of the head, printing a nozzle check pattern on the coated paper at a driving frequency of 20 kHz, and discharging the print pattern Or, the number of discharge deviations was confirmed.

◯: Number of discharge omissions and deviations is 2 or less △: Number of ejection omissions and deviations is 3 to 5
X: The number of discharge omissions and twists is 6 or more

<Production of Evaluation Fabric_Inkjet Printing>
Using a piezo-type inkjet head, the printing agent was purged onto the head, the nozzle surface of the head was wiped, and then printed on cotton broad (manufactured by Color Printing Co., Ltd.) at a driving frequency of 10 kHz. Each printing agent was printed on the cotton fabric, dried at 100 ° C. for 1 minute, and heat-treated at 150 ° C. for 5 minutes.

<Evaluation of washing resistance>
After testing in accordance with method A-2 of JIS L 0844: 2005, the grades were graded from 1 to 5 according to the criteria for visual perception using the gray scale for fading color of JIS L 0801: 2004. Judged. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

<Evaluation of friction resistance>
In accordance with JIS L 0849: 2004, after performing dry and wet tests using a Gakushin type friction fastness tester, a visual method using a gray scale for fading color of JIS L 0801: 2004 The grades were judged from 1st grade to 5th grade according to the criteria. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

Tables 1 to 3 show the compositions of printing agents composed of the water-based inks of Examples and Comparative Examples and various evaluation results.

From the results of Tables 1 to 3, the printing agents of the present invention (Examples 1 to 17) have good continuous ejection properties and high frequency ejection properties, and are resistant to washing and friction when printed on a fabric. It is possible to achieve both.

1: T-shaped micromixer M1
2: T-shaped micromixer M2
3: T-shaped micromixer M3
4: Tube reactor R1
5: Tube reactor R2
6: Tube reactor R3
7: Tube reactor P1 for pre-cooling
8: Tube reactor P2 for pre-cooling
9: Tube reactor P3 for pre-cooling
10: Tube reactor P4 for pre-cooling

Claims (10)

1. The dynamic surface tension measured by the maximum bubble pressure method at a surface lifetime of 20 milliseconds is 38 mN / m or more and 60 mN / m or less, and the static surface tension measured by the Wilhelmy method is 32 mN / m or more and 42 mN / m or less. A printing agent characterized by being.
2. 2. The printing agent according to claim 1, wherein the dynamic surface tension measured by the maximum bubble pressure method at a surface lifetime of 1000 milliseconds is 33 mN / m or more and 48 mN / m or less.
3. The printing agent according to claim 2, wherein a difference between the dynamic surface tension at the surface life of 20 milliseconds and the dynamic surface tension at the surface life of 1000 milliseconds is less than 15 mN / m.
4. 4. The method according to claim 1, wherein the printing agent contains a surfactant, and the surfactant is contained in the range of 0.1% by mass to 2.5% by mass with respect to the total amount of the printing agent. The printing agent according to item.
5. The printing agent according to claim 4, wherein the surfactant is an acetylene glycol surfactant or a silicone surfactant.
6. The printing agent according to any one of claims 1 to 5, wherein the printing agent further contains a binder, and the binder is a resin having a glass transition temperature of 0 ° C or lower.
7. The printing agent according to claim 6, wherein the printing agent contains a colorant and a dispersion resin, and the dispersion resin is a urethane resin or an acrylic resin.
8. The printing agent according to claim 6 or 7, wherein a mass ratio [dispersion resin / binder] of the dispersion resin and the binder is in a range of 0.06 to 1.
9. A printing agent for ink jet recording comprising the printing agent according to any one of claims 1 to 8.
10. A printed matter in which the printing agent according to any one of claims 1 to 9 is printed on a fabric.

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