WO2020080122A1 - Method for producing printed object - Google Patents

Abstract

The present invention addresses the problem of providing ink that has: excellent image quality without streaking, etc. even when, for example, the gap between the surface of a fabric and an inkjet head is wide; and water-fastness such that color fading, transfer, peeling, etc. do not occur even when printed fabric is washed or rubbed. The present invention relates to a method for producing a printed object that is characterized by comprising a printing step for obtaining a printed object by printing ink on a fabric using an inkjet printing method, wherein the shortest distance between the ink discharging port of an inkjet head and the fabric in the printing step is at least 2 mm, and the ink has a viscosity of not more than 20 mPa∙s and surface tension in the range of 20–40 mN/m.

Description

Printed matter manufacturing method

The present invention relates to an inkjet recording method and a method for producing a printed matter.

In recent years, due to the technological evolution of inkjet recording methods, digitalization by inkjet is progressing from conventional analog methods such as screen printing. Just as printers for plain paper and inkjet paper have become widespread in general households, the application is expanding to various base materials for industrial use as well. Development is expanding with inkjet printers. Further, in textile printing for printing images such as characters, pictures, and patterns on a textile substrate such as cotton knit and non-woven fabric used for fabrics and T-shirts, clothes, curtains, covers, Methods for manufacturing textile products for home textiles such as sheets are being studied. In order to apply the ink jet recording method to these cloths, it is necessary to achieve both print quality and performance such as washing resistance and abrasion resistance of the printed textile cloth. However, if the distance between the inkjet head and the cloth, that is, the so-called gap is widened, the flight bending of the ejected ink droplets and the deviation of the landing position are likely to occur, which causes a problem that a predetermined image quality cannot be obtained.

Therefore, even if the gap is wide, there is a demand for ink that has less landing position deviation and that the printed fabric after printing has good washing resistance and abrasion resistance.

When printing with the inkjet recording method on the surface of the cloth, usually, due to the fluff on the surface of the cloth, the thickness of the cloth, and the surface unevenness, if the inkjet head and the cloth come into contact with each other even for a moment, ejection failure will occur. Therefore, in order to prevent contact between the cloth surface and the inkjet head, it is required to secure a gap of preferably 2 mm or more, more preferably 3 mm or more.

However, when the gap is widened, generally, the distance until the ink ejected from the ink ejection port of the ink jet head reaches the surface of the fabric is long, and thus the flight curve of the ink droplets that may occur during the landing is reduced. Misalignment of the landing position is likely to occur. Further, as the distance becomes long, the ejection speed due to the air resistance also decreases, so that the spread of the ink on the surface of the cloth is insufficient, which may cause a defect in the image quality such as streaks on the printed matter.

JP, 2011-12226, A

The problem to be solved by the present invention is, for example, even when the gap between the surface of the fabric and the inkjet head is wide, it is possible to produce a printed matter with excellent image quality without streaks, and to wash or scratch the printed matter. It is an object of the present invention to provide a method for producing a printed matter having a level of washing resistance and abrasion resistance that does not cause color fading, color transfer, peeling, etc.

The present invention comprises a printing step of obtaining a printed matter by printing ink on a cloth by an ink jet recording method, and in the printing step, the shortest distance between the ink ejection port of the inkjet head and the cloth is 2 mm or more. The present invention relates to a method for producing a printed matter, wherein the size of each ink droplet ejected from the head is in the range of 10 to 50 pl.

With the ink of the present invention, even when the distance between the surface of the cloth and the inkjet head is long, it is possible to produce a printed matter having a desired image quality without printing streaks. Therefore, clothes, curtains, covers, It can be suitably used for manufacturing textile products for home textiles such as sheets.

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

The method for producing a printed matter according to the present invention comprises a printing step of obtaining a printed matter by printing ink on a cloth by an inkjet recording method, and in the printing step, the shortest distance between the ink ejection port of the inkjet head and the cloth is 2 mm or more. The size of each ink droplet ejected from the inkjet head is in the range of 10 to 50 pl.

The shortest distance is a distance from a surface (x) having an ink ejection port of an inkjet head to a position (y) where a perpendicular line of the surface (x) (a perpendicular line assumed to the surface (x)) and a cloth intersect. (Gap).

In the inkjet recording method applied in the method for producing a printed matter of the present invention, an inkjet recording apparatus having a configuration in which the shortest distance (gap) is 2 mm or more, preferably 3 mm or more can be used.

The shortest distance prevents contact between the surface (recording surface) of the cloth and the ink discharge port even if the cloth has a large fluff or unevenness, and damage to the ink discharge port or the ink Ink ejection failure due to deterioration of water repellent function, which is often provided in the ejection port, is effectively prevented, and even if the distance between the surface of the cloth and the inkjet head is long, printed matter having no streak can be obtained. In manufacturing, the lower limit of the distance is preferably 3 mm or more, and the upper limit of the distance is preferably 10 mm or less, particularly preferably 5 mm or less.

At the shortest distance, the lower limit of the size of ink droplets ejected from the inkjet head is preferably 10 pl, more preferably 15 pl, even more preferably 20 pl, and the upper limit is preferably 50 pl, more preferably It is preferable that it is 45 pl, and more preferably 40 pl, in order to produce a printed matter having excellent image quality without streaks and to obtain a printed matter having further excellent wash resistance.

As the ink that can be used in the inkjet recording method, for example, it is preferable to use an ink having a viscosity at 30 ° C. of 20 mPa · s or less and a surface tension of 20 mN / m to 40 mN / m.

The ink may have a viscosity lower limit at 30 ° C. of preferably 4 mPa · s or more, more preferably 6 mPa · s or more, and further preferably 8 mPa · s or more. it can. On the other hand, the upper limit of the viscosity of the ink at 30 ° C. is preferably 20 mPa · s or less, more preferably less than 15 mPa · s, and further preferably 12 mPa · s. The following can be used:

The ink having a viscosity in the above range has a sufficient volume of droplets ejected from the inkjet head, and therefore the perpendicular line of the surface (x) and the cloth are separated from the surface (x) having the ink ejection port of the inkjet head. Even if the distance to the intersecting position (y) is 2 mm or more, it is possible to apparently reduce the deviation of the landing position on the fabric caused by flight bending, and it is possible to effectively prevent the generation of streaks on the printed matter.

Further, an ink having a viscosity in the above range is more excellent in storage stability and ejection stability of the ink, and thus can be suitably used for printing by an inkjet method, for example.

The viscosity of the ink was measured under the following conditions using a cone-plate (cone-plate) rotational viscometer corresponding to an E-type viscometer.
Measuring device: TVE-25 type viscometer (manufactured by TVE-25 L)
Calibration standard solution: JS20
Measurement temperature: 32 ° C
Rotation speed: 10-100 rpm
Injection volume: 1200 μL

Further, the ink may have a lower limit of surface tension at 25 ° C. of preferably 20 mN / m or more, more preferably 25 mN / m or more, further preferably 28 mN / m or more. can do. On the other hand, the upper limit of the surface tension of the ink at 25 ° C. is preferably 40 mN / m or less, more preferably 38 mN / m or less, and further preferably 36 mN / m or less.

The ink having the surface tension in the above range has good wettability of the discharged droplets on the fabric surface, and has sufficient wetting and spreading after landing. As a result, even if the distance from the surface (x) having the ink ejection ports of the inkjet head to the position (y) where the perpendicular line of the surface (x) and the cloth intersect is 2 mm or more, flight deflection of the ejected droplets. It is possible to apparently reduce the deviation of the landing position on the cloth caused by the above, and to effectively prevent the generation of streaks in the printed matter.

The surface tension of the ink means a value measured under the following conditions using an automatic surface tension meter to which the Wilhelmi method is applied. According to the Wilhelmy method, the static surface tension and the dynamic surface tension can be measured, but the surface tension of the ink in the present invention represents the value of the static surface tension.
Measuring device: Automatic surface tensiometer (Kyowa Interface Science Co., Ltd., CBVP-Z type)
Measurement temperature: 25 ° C
Stylus: platinum plate

As the ink, any ink having the above-mentioned viscosity and surface tension can be used. For example, an ink containing a solvent such as an aqueous medium (C) and a coloring material (B) is used. You can Among them, as the ink, it is preferable to use an ink further containing a binder resin (A) in order to obtain a printed matter having excellent washing resistance and abrasion resistance.

As the ink, it is preferable to use one in which the binder resin (A), the coloring material (B), and the like exist in a state of being dissolved or dispersed in an aqueous medium (C) which is a solvent.

The binder resin (A) is used to fix the pigment on the recording medium. In particular, in the case of printing on a cloth, the use of an ink containing a large amount of the binder resin (A) improves the washing resistance and abrasion resistance (wet type, dry type) of the printed matter, while making the texture of the cloth slightly hard. There is a tendency. Therefore, the binder resin (A) is preferably used in the range of 20% by mass or less, more preferably 15% by mass or less with respect to the total mass of the ink, and the lower limit thereof is 1% by mass or more. 5 mass% or more is more preferable in order to obtain a printed matter excellent in washing resistance and abrasion resistance.

The binder resin (A) is for fixing the color material (B) such as a pigment onto the cloth as described above. When a binder resin having a glass transition temperature exceeding room temperature is used, the texture of the fabric tends to be slightly hard. Therefore, as the binder resin (A), it is particularly preferable to use one having a glass transition temperature of 0 ° C. or less, which maintains good texture and washing resistance even when the ink or printed matter is used in a low temperature region. It is preferable to

The ratio of the binder resin (A) to the color material (B) may be a ratio that is usually used in ink, for example, the ratio of the binder resin (A) to the color material = 1: 3 to 8. The range of: 1 is preferable, and the range of 1: 2 to 3.5: 1 is more preferable in order to obtain a printed matter having further excellent abrasion resistance. Further, as the binder resin (A), it is preferable to use a binder resin having a large weight average molecular weight in order to obtain a printed matter having further excellent abrasion resistance, and to impart even more excellent dischargeability. Above, it is preferable to use a binder resin having a weight average molecular weight of 200,000 or less.

Examples of the binder resin (A) include urethane resins, polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymers, potassium acrylate-acrylonitrile copolymers, vinyl acetate-acrylic acid ester copolymers. Polymers, acrylic copolymers such as acrylic acid-acrylic acid alkyl ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid alkyl ester copolymers, styrene Styrene-acrylic acid resins such as -α-methylstyrene-acrylic acid copolymer and styrene-α-methylstyrene-acrylic acid-acrylic acid alkyl ester copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene -Acry Acid copolymer; 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 Coalescence, vinyl acetate-based copolymers such as vinyl acetate-acrylic acid copolymer, and salts thereof can be used.

Above all, it is preferable to use a urethane resin or an acrylic resin as the binder resin because it is easily available and improves the abrasion resistance of the printed matter, and particularly, the wash resistance (wash fastness) of the printed matter on the cloth. Degree) and friction resistance (fastness to dry friction and fastness to wet friction).

The urethane resin includes one or more polyols selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols, 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 a polyisocyanate is used.

The weight average molecular weight of the urethane resin is preferably from 5,000 to 200,000, more preferably from 20,000 to 150,000, in order to further improve the abrasion resistance of the printed matter.

Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, Glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, femmellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, 1,2,3-propane Compounds having two or more active hydrogen groups such as trithiol, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydride Emissions, 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 a diol compound, dicarboxylic acid, hydroxycarboxylic acid compound, etc., ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymerization of polyester obtained by these reactions. To be Examples of the diol compound as a raw material of this polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 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 their alkylene oxide adducts.

Examples of the dicarboxylic acid as the raw material of 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 can be mentioned.

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

As the polycarbonate polyol, for example, one obtained by reacting a carbonic acid ester with a low molecular weight polyol, preferably a linear aliphatic diol can be used.

As the carbonic acid ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, etc. can be used.

Examples of the low molecular weight polyol capable of reacting with the carbonic acid ester 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, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4 -Cyclohexanedimethanol, hydroquinone, resor Relatively low molecular weight dihydroxy compounds such as amine, bisphenol-A, bisphenol-F and 4,4'-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol, polyhexamethylene adipate, Polyester polyols such as polyhexamethylene 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 producing the polycarbonate-based urethane resin.

Also, the urethane resin has a hydrophilic group for imparting dispersion stability in the ink.

As the hydrophilic group, those generally referred to as anionic groups, cationic groups, and nonionic groups can be used, but among them, it is preferable to use anionic groups and cationic groups.

As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group or the like can be used, and among them, a carboxylate group partially or wholly neutralized with a basic compound or the like, or The use of sulfonate groups is preferred for maintaining good water dispersibility.

Examples of the basic compound that can be used for neutralizing the carboxyl group or the sulfonic acid group as the anionic group include, for example, ammonia, triethylamine, pyridine, organic amines such as morpholine, alkanolamines such as monoethanolamine, Na, and the like. Examples thereof include metal base compounds containing K, Li, Ca and the like. 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.

Also, as the cationic group, for example, a tertiary amino group or the like can be used. Examples of acids that can be used when neutralizing a part or all of the tertiary amino groups include formic acid, acetic acid, and the like. Further, as the quaternizing agent that can be used when a part or all of the tertiary amino groups is quaternized, 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. Above all, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve hydrophilicity.

It is preferable that the hydrophilic group is present in an amount of 0.5% by mass to 30% by mass with respect to the total amount of the urethane resin, which imparts better water dispersibility, and is in the range of 1% by mass to 20% by mass. More preferable.

Further, the ink of the present invention may use a crosslinking agent described later for the purpose of further improving abrasion resistance. When the cross-linking agent is used, it is preferable to use, as the urethane resin, one having a functional group capable of undergoing a cross-linking reaction with the functional group of the cross-linking agent.

Examples of the functional group include a carboxyl group and a carboxylate group that can be used as the hydrophilic group. The carboxyl group and the like contribute to the water dispersion stability of the urethane resin in an aqueous medium, and when they undergo a crosslinking reaction, they also act as the functional group and can partially crosslink 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 it is preferable to use a urethane resin having an acid value of 15 to 50. It is preferable in improving. The acid value referred to in the present invention is a theoretical value calculated based on the amount of the acid group-containing compound such as the carboxyl group-containing polyol used in the production of the 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, polyamine and other compounds containing active hydrogen atom 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 and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; di-succinate Dolazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate ester, semicarbazid-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, preferably ethylenediamine.

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

The chain extender, for example, the equivalent of the amino group and the active hydrogen atom-containing group of the chain extender, relative to the equivalent of isocyanate groups of the 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), and more preferably 0.5% by mass.

The chain extender can be used when the polyol is reacted with the polyisocyanate or after the reaction. The chain extender can be used when the urethane resin obtained above is dispersed in an aqueous medium to make it aqueous.

Examples of polyols other than those mentioned above include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 , 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 alkylene oxide adducts thereof, glycerin, trimethylolethane, trimethylolpropane, sorbitol, Relatively low molecular weight polyol of pentaerythritol, and the like. These polyols may 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, and hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as diisocyanate, xylylene diisocyanate, and tetramethyl xylylene diisocyanate can be used alone or in combination of two or more.

The acrylic resin that can be used as the binder resin (A) is not particularly limited, and is a resin obtained by homopolymerizing or copolymerizing (meth) acrylate and copolymerizing a vinyl monomer copolymerizable with (meth) acrylate. Can be given. In the present invention, "(meth) acrylic acid" means methacrylic acid or acrylic acid, "(meth) acrylate" means methacrylate or acrylate, and "(meth) acryloyl" means methacryloyl or acryloyl. Refers to.

Examples of (meth) acrylate and vinyl monomers copolymerizable with (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t. -Alkyl (meth) acrylates such as butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate; 2-hydrodoxyethyl (meth) acrylate A hydroxyl group-containing monomer such as 2-hydroxypropyl (meth) acrylate; an alkyl polyalkylene glycol mono (meth) such as methoxy polyethylene glycol mono (meth) acrylate or methoxy polypropylene 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.), vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, etc. Vinyl compound; 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; , 3-Butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-cyclohexadiene and other conjugated dienes Is mentioned. These monomers may be used alone or in combination of two or more.

As 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 monomers, in order to improve the texture of a printed matter. Examples of the monomer having such a functional group include a monomer having a carboxyl group, a monomer having an epoxy group, a monomer having a hydrolyzable silyl group, a monomer having an amide group, and the like.

As the monomer having a carboxyl group, for example, (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, citraconic acid, etc. 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) acryloyloxypropyltriene. (Meth) acryloyloxyalkylsilane compounds such as methoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane Can be used. These monomers may be used alone or in combination of two or more.

As the monomer having an amide group, an acrylamide compound such as (meth) acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, diacetoneacrylamide; or the like can be used.

The form of dispersion of the acrylic resin in water is not particularly limited, and examples thereof include an emulsion forcibly emulsified with an emulsifier and a dispersion having a nonionic group or a neutralized ionic group in the resin. Particularly, as the acrylic resin, a dispersion obtained by neutralizing an acrylic resin having a carboxyl group with a basic compound is preferable. As the basic compound, the same basic compounds as those exemplified as being usable for neutralizing the carboxyl groups and the like of the urethane resin can be used.

As the coloring material (B) usable in the ink of the present invention, known and commonly used pigments and dyes can be used. Above all, it is preferable to use a pigment for producing a printed matter having excellent weather resistance and the like. Further, as the color material (B), a colorant in which the pigment is coated with a resin can be used.

The pigment is not particularly limited, and organic pigments or inorganic pigments that are commonly used in conventional screen printing or water-based inkjet recording inks can be used.

As the pigment, both non-acid-treated pigment and acid-treated pigment can be used, and both dry powder and wet cake can be used.

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

Examples of the organic pigment include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofuraron pigments, etc.), lake pigments (eg, basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

Specific examples of the above pigment include No. manufactured by Mitsubishi Chemical Co., Ltd. if it is a pigment used for 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 Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 etc. made by Colombia, Regal 400R, Regal 330R, Regul 660R made by Cabot. 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are manufactured by Degussa Color Black FW1, FW2, FW2V, FW200, nt200, 160S, S150, S150, S150, S150, S150, S150, S150, S150, S150, S150, S150. Same U, Same V, Same 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 pigments thereof. Examples thereof include a mixture or solid solution of at least two kinds of pigments selected from

Specific examples of pigments used in 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. Pigment Red 17, 49: 2, 112, 149, 150, 177, 178, 179, 188, 254, 255 and 264 are preferably used alone or in combination of two or more.

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.

Further, specific examples of pigments that can be used in the white ink include sulfates of alkaline earth metals, carbonates, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, hydrated alumina, Examples thereof include titanium oxide, zinc oxide, talc and clay. These may be surface-treated.

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

It is preferable that a means for properly dispersing the pigment in the aqueous medium (C) is provided so that the pigment can be stably present in the ink.

Examples of the means include (i) a method of dispersing a pigment together with a pigment dispersant in an aqueous medium (C) by a dispersion method described later (ii) a dispersibility-imparting group (hydrophilic functional group and / or The salt thereof) may be directly or indirectly bonded via an alkyl group, an alkyl ether group, an aryl group or the like to disperse and / or dissolve the self-dispersion pigment in the aqueous medium (C).

As the self-dispersion pigment, for example, a pigment obtained by subjecting the pigment to physical treatment or chemical treatment to bond (graft) a dispersibility imparting group or an active species having a dispersibility imparting group to the surface of the pigment is used. be able to. The self-dispersion pigment is, for example, a vacuum plasma treatment, an oxidation treatment with hypohalous acid and / or a hypohalite salt, an oxidation treatment with ozone, or a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water. Alternatively, it can be produced by a method in which p-aminobenzoic acid is bonded to the surface of the pigment to bond the carboxyl group via the phenyl group.

Since the water-based ink containing the self-dispersion pigment does not need to contain the pigment dispersant, there is almost no foaming due to the pigment dispersant and it is easy to prepare an ink having excellent ejection stability. Further, the water-based ink containing the self-dispersion type pigment is easy to handle, and it is possible to contain a larger amount of the pigment because a large increase in the viscosity due to the pigment dispersant is suppressed. Can be used for

As the self-dispersion pigment, a commercially available product may be used. Examples of such a commercially available product include Microjet CW-1 (trade name; manufactured by Orient Chemical Industry Co., Ltd.), CAB-O-JET200, CAB-O-JET300 (the above trade name; manufactured by Cabot Corporation) can be mentioned.

In the present invention, if the composition of the ink is excessively changed in order to prevent the deterioration of the image quality such as the streaks, the print density and wash resistance of the printed matter may tend to be reduced. The color material (B) prevents generation of the streaks, maintains excellent dispersion stability of the color material (B), and improves print density and wash resistance of printed matter. Is preferably used in the range of 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass.

(Pigment dispersant)
The pigment dispersant can be preferably used when a pigment is used as the coloring material (B).

Examples of the pigment dispersant include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid. -Acrylic ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer and other styrene-acrylic resins, styrene-maleic acid copolymer A combined resin, an aqueous resin of a styrene-maleic anhydride copolymer, a vinylnaphthalene-acrylic acid copolymer, and a salt of the above aqueous resin can be used. As the pigment dispersant, Ajinomoto Fine Techno Co., Ltd.'s Azisper PB series, Big Chemie Japan's Disperbyk series, BASF's EFKA series, Nippon Lubrizol's SOLSPERSE series, Evonik's product The TEGO series etc. of can be used.

As the pigment dispersant, a polymer (G) described below is used in order to significantly reduce coarse particles and, as a result, to impart good ejection stability required when the ink is ejected by an inkjet method. Is preferred.

As the polymer (G), those having an anionic group can be used, and among them, the solubility in water is 0.1 g / 100 ml or less, and depending on the basic compound of the anionic group, It is preferable to use a polymer having a number average molecular weight in the range of 1000 to 6000, which is capable of forming fine particles in water when the sum ratio is 100%.

The solubility of the polymer (G) in water was defined as follows. That is, 0.5 g of the polymer (E) having a particle size adjusted in the range of 250 μm to 90 μm using a sieve with openings of 250 μm and 90 μm is enclosed in a bag processed with a 400 mesh wire mesh, dipped in 50 ml of water and kept at 25 ° C. The mixture was left under gentle stirring for 24 hours under temperature. After soaking for 24 hours, a 400-mesh wire net enclosing the polymer (E) was dried for 2 hours by a dryer set at 110 ° C. The change in weight of a 400-mesh wire net enclosing the polymer (E) before and after immersion in water was measured, and the solubility was calculated by the following formula.

Further, in the present invention, whether or not to form fine particles in water when the neutralization rate of the anionic group with the basic compound is 100% was judged as follows.
(1) The acid value of the polymer (G) is previously measured by an acid value measuring method based on JIS test method K 0070-1992. Specifically, 0.5 g of the polymer (G) is dissolved in tetrahydrofuran and titrated with 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator to determine the acid value.
(2) To 50 ml of water, 1 g of the polymer (G) is added, and then a 0.1 mol / L potassium hydroxide aqueous solution is added to just neutralize the obtained acid value by 100% to make 100% neutralization.
(3) The 100% neutralized solution was irradiated with ultrasonic waves at a temperature of 25 ° C. for 2 hours in an ultrasonic cleaner (SND Corp. ultrasonic cleaner US-102, 38 kHz self-oscillation). Then leave at room temperature for 24 hours.

After standing for 24 hours, a sample liquid obtained by sampling a liquid at a depth of 2 cm from the liquid surface was used as a dynamic light scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., dynamic light scattering type particle size measuring device “micro”). By using a track particle size distribution analyzer UPA-ST150 "), it is confirmed whether or not the fine particles are present by determining whether or not the light scattering information by the fine particle formation can be obtained.

In order to further improve the stability of the fine particles formed by the polymer (G) used in the present invention in water, the particle diameter of the fine particles is preferably in the range of 5 nm to 1000 nm, and is in the range of 7 nm to 700 nm. More preferably, it is most preferably in the range of 10 nm to 500 nm. Further, the smaller the particle size distribution of the fine particles, the more excellent the dispersion stability tends to be. However, even when the particle size distribution is wide, it is possible to obtain the ink having the dispersion stability superior to the conventional one. The particle size and particle size distribution are determined by a dynamic light scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd. dynamic light scattering type particle size measuring device “Microtrac particle size distribution meter UPA”, similar to the method for measuring the fine particles. -ST150 ").

The neutralization rate of the polymer (G) used in the present invention was determined by the following formula.

The acid value of the polymer (G) was measured based on JIS test method K0070-1992. Specifically, it was determined by dissolving 0.5 g of the sample in tetrahydrofuran and titrating with 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.

The number average molecular weight of the polymer (G) is preferably in the range of 1000 to 6000, more preferably 1300 to 5000, and more preferably 1500 to 4500 in the aqueous medium (C). It is more preferable to effectively suppress the aggregation of the coloring material (B) and the like, and to obtain an ink having good dispersion stability of the coloring material (B).

Note that the number average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography), and specifically, a value measured under the following conditions.

(Method of measuring number average molecular weight (Mn))
The measurement was carried out by the gel permeation chromatography (GPC) method under 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 and used.

"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSK gel G4000" (7.8 mm ID x 30 cm) x 1 "TSK gel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
(Standard polystyrene)
Tosoh Corporation "TSK gel standard polystyrene A-500"
Tosoh Corporation “TSKgel Standard Polystyrene A-1000”
Tosoh Corporation "TSK gel standard polystyrene A-2500"
Tosoh Corporation “TSKgel Standard Polystyrene A-5000”
"TSK gel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSK gel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSK gel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSK gel standard polystyrene F-10" manufactured by Tosoh Corporation
Tosoh Corporation "TSK gel standard polystyrene F-20"
"TSK gel standard polystyrene F-40" manufactured by Tosoh Corporation
Tosoh Corporation “TSK gel standard polystyrene F-80”
Tosoh Corporation "TSK gel standard polystyrene F-128"
Tosoh Corporation "TSK gel standard polystyrene F-288"
Tosoh Corporation "TSK gel standard polystyrene F-550"

As the polymer (G), the surface tension of the ink containing the polymer (G) is preferably 30 dyn / cm or more, more preferably 40 dyn / cm or more, and 65 dyn / cm to 75 dyn / cm close to the surface tension of water. It is particularly preferred to use The surface tension is obtained by adding 1 g of the polymer (G) to water, and then adding a 0.1 mol / L potassium hydroxide aqueous solution, which is 100% neutralized to the obtained acid value, to obtain a 100% neutralized polymer solution. Is the value measured for.

As the polymer (G), a polymer that is insoluble or sparingly soluble in water in a non-neutralized state and forms fine particles in a 100% neutralized state can be used. The polymer is not particularly limited as long as it is a polymer having a hydrophobic group in one molecule in addition to a certain anionic group.

As such a polymer, a block polymer having a polymer block having a hydrophobic group and a polymer block having an anionic group can be mentioned. In the polymer (G), the number of the anionic groups and the solubility in water are not necessarily specified by the acid value or the number of the anionic groups when designing the polymer. For example, in the case of polymers having the same acid value, However, those having a low molecular weight tend to have high solubility in water, and those having a high molecular weight tend to have low solubility in water. From this, in the present invention, the polymer (G) is specified by the solubility in water.

The polymer (G) may be a homopolymer, but is preferably a copolymer, and may be a random polymer, a block polymer, or an alternating polymer, and among them, a block polymer. It is preferable. The polymer may be a branched polymer, but is preferably a linear polymer.

Further, the polymer (G) is preferably a vinyl polymer in terms of design freedom, and as a method for producing a vinyl polymer having a desired molecular weight and solubility characteristics in the present invention, living radical polymerization, living cationic polymerization are used. It is preferable to manufacture by using "living polymerization" such as living anionic polymerization.

Among them, the polymer (G) is preferably a vinyl polymer produced by using a (meth) acrylate monomer as one of the raw materials, and as a production method of such a vinyl polymer, living radical polymerization, living anion polymerization are used. Is preferable, and living anionic polymerization is preferable from the viewpoint that the molecular weight of the block polymer and each segment can be designed more precisely.

The polymer (G) produced by living anionic polymerization is specifically a polymer represented by the general formula (3).

In the general formula (3), A ¹ represents an organolithium initiator residue, A ² represents a polymer block having a hydrophobic group, A ³ represents a polymer block containing an anionic group, and n is 1 to 5 Represents an integer, and B represents an aromatic group or an alkyl group.

In general formula (3), A ¹ represents an organolithium initiator residue. Specific examples of the organic lithium initiator include methyl lithium, ethyl lithium, propyl lithium, butyl lithium (n-butyl lithium, sec-butyl lithium, iso-butyl lithium, tert-butyl lithium, etc.), pentyl lithium, hexyl lithium, Alkyl lithium such as methoxymethyl lithium and ethoxymethyl lithium; phenyl lithium lithium such as benzyl lithium, α-methyl styryl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,1-diphenylhexyl lithium and phenylethyl lithium Alkenyl lithium such as vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium; ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium, etc. Ruquinyl lithium; aryl lithium such as phenyl lithium and naphthyl lithium; heterocyclic lithium such as 2-thienyl lithium, 4-pyridyl lithium and 2-quinolyl lithium; alkyl such as tri (n-butyl) magnesium lithium and trimethyl magnesium lithium Examples thereof include lithium magnesium complex.

In the organic lithium initiator, the bond between the organic group and lithium is cleaved to generate an active terminal on the organic group side, and the polymerization is started from there. Therefore, the organic group derived from organolithium is bonded to the terminal of the obtained polymer. In the present invention, the organic group derived from organolithium bonded to the polymer terminal is referred to as an organolithium initiator residue. For example, in the case of a polymer using methyllithium as an initiator, the organolithium initiator acid group becomes a methyl group, and in the case of a polymer using butyllithium as an initiator, the organolithium initiator acid group becomes a butyl group.

In the general formula (3), A ² represents a polymer block having a hydrophobic group. A ² is another object to balance balance described above moderate solubility, it is preferably a high adsorption to the pigment group when in contact with the pigment, from the viewpoints, A ² is an aromatic ring or It is preferably a polymer block of a monomer having a heterocycle.
The polymer block of a monomer having an aromatic ring or a heterocyclic ring is specifically a homopolymerization or copolymerization of a monomer having an aromatic ring such as a styrene-based monomer or a monomer having a heterocyclic ring such as a vinylpyridine-based monomer. It is a polymer block of a homopolymer or a copolymer obtained as described above.

Examples of the monomer having an aromatic ring include styrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-tert-butoxystyrene, m-tert-butoxystyrene, Styrene-based monomers such as p-tert- (1-ethoxymethyl) styrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, α-methylstyrene, p-methyl-α-methylstyrene and vinylnaphthalene , Vinyl anthracene and the like.

Further, examples of the monomer having a heterocycle include vinylpyridine-based monomers such as 2-vinylpyridine and 4-vinylpyridine. These monomers may be used alone or in admixture of two or more.

In the general formula (3), A ³ represents a polymer block containing an anionic group. A ³ has the purpose of imparting appropriate solubility as described above, and the purpose of imparting dispersion stability in water when it becomes a pigment dispersion.
Examples of the anionic group in the polymer block A ³ include a carboxyl group, a sulfonic acid group, a phosphoric acid group and the like. Of these, a carboxyl group is preferable because of its preparation, the abundance of monomer varieties, and easy availability. Further, two carboxyl groups may be an acid anhydride group which is dehydration-condensed in the molecule or between the molecules.

The method for introducing the anionic group of A ³ is not particularly limited. For example, when the anionic group is a carboxyl group, a homopolymer obtained by homopolymerization of (meth) acrylic acid or copolymerization with another monomer, or It may be a polymer block (PB1) of a copolymer, or may be a homopolymer obtained by homopolymerizing or copolymerizing (meth) acrylate having a protective group which is a renewable anionic group by deprotection. The polymer block or the copolymer may be a polymer block (PB2) in which some or all of the protective groups that can be regenerated to the anionic group are regenerated to anionic groups.

The (meth) acrylic acid used in the polymer block A ³ is a generic term for acrylic acid and methacrylic acid, and the (meth) acrylate is a generic term for acrylate and methacrylate.

Specific examples of (meth) acrylic acid and (meth) acrylate include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, iso-propyl (meth) acrylate, and (meth). Allyl acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, ( Iso-amyl methacrylic acid, n-hexyl (meth) acrylic acid, n-octyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, n-lauryl (meth) acrylic acid, n-methacrylic acid n -Tridecyl, n-stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acryl Cyclohexylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl acrylate (meth) acrylate , Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth) acrylic Acid diethylaminoethyl, (meth) acrylic acid trifluoroethyl, (meth) acrylic acid tetrafluoropropyl, (meth) acrylic acid pentafluoropropyl, (meth) acrylic acid octafluoropentyl, (meth) acrylic acid pentadecafluorooctyl, (Meth) acrylic Heptadecafluorodecyl, N, N-dimethyl (meth) acrylamide, (meth) acryloylmorpholine, (meth) acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, Polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (Meth) acrylate, lauroxy polyethylene glycol ( (Meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxy polyethylene glycol-polypropylene glycol (meth) acrylate and other polyalkylene oxide group-containing (meth) Examples include acrylate. These monomers may be used alone or in admixture of two or more.

In the living anionic polymerization method, when the monomer to be used is a monomer having a group having an active proton such as an anionic group, the active end of the living anion-polymerized polymer immediately reacts with a group having these active protons and is deactivated. Polymer cannot be obtained. In living anionic polymerization, it is difficult to polymerize a monomer having a group having an active proton as it is. Therefore, polymerization is performed in a state in which the group having an active proton is protected, and then the protective group is deprotected to have an active proton. It is preferred to regenerate the group.

For this reason, it is preferable to use a monomer containing a (meth) acrylate having a protective group which is a reproducible anionic group in the polymer block A ³ by deprotection. By using the monomer, the above-mentioned inhibition of the polymerization can be prevented during the polymerization. The anionic group protected by the protective group can be regenerated into an anionic group by deprotecting the block polymer after it is obtained.

For example, when the anionic group is a carboxyl group, the carboxyl group can be regenerated by esterifying the carboxyl group and deprotecting it by hydrolysis or the like as a subsequent step. In this case, the protective group that can be converted into a carboxyl group is preferably a group having an ester bond, and examples thereof include primary alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, and n-butoxycarbonyl group. A secondary alkoxycarbonyl group such as an isopropoxycarbonyl group or a sec-butoxycarbonyl group; a tertiary alkoxycarbonyl group such as a t-butoxycarbonyl group; a phenylalkoxycarbonyl group such as a benzyloxycarbonyl group; an ethoxyethylcarbonyl group or the like And an alkoxyalkylcarbonyl group of

When the anionic group is a carboxyl group, usable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec. -Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate ) Acrylate), tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate ) Acrylate), nonadecyl (meth) acrylate, icosanyl (meth) acrylate and other alkyl (meth) acrylates; benzyl (meth) acrylate and other phenylalkylene (meth) acrylates; ethoxyethyl (meth) acrylate and other alkoxyalkyl (meth) acrylates Examples thereof include acrylate. These (meth) acrylates may be used alone or in combination of two or more. Further, among these (meth) acrylates, t-butyl (meth) acrylate and benzyl (meth) acrylate are preferably used because the conversion reaction to the carboxyl group is easy. Further, in consideration of industrial availability, t-butyl (meth) acrylate is more preferable.

In the general formula (3), B represents an aromatic group or an alkyl group having 1 to 10 carbon atoms. N represents an integer of 1 to 5.

In the living anionic polymerization method, when it is attempted to directly polymerize a (meth) acrylate monomer on the active end of a styrene-based polymer having strong nucleophilicity, there are cases where carbonyl carbon cannot be polymerized due to nucleophilic attack. Therefore, when the (meth) acrylate monomer is polymerized to A ¹ -A ² , a reaction modifier is used to adjust the nucleophilicity, and then the (meth) acrylate monomer is polymerized. B in the general formula (3) is a group derived from the reaction modifier. Specific examples of the reaction modifier include diphenylethylene, α-methylstyrene, p-methyl-α-methylstyrene and the like.

The living anion polymerization method can be carried out by adjusting the reaction conditions by a batch method as used in conventional free radical polymerization, or a method of continuously polymerizing by a microreactor can be mentioned. Since the microreactor has a good mixing property of the polymerization initiator and the monomer, the reactions start at the same time, the temperature is uniform, and the polymerization rate can be made uniform, so that the molecular weight distribution of the polymer to be produced can be narrowed. At the same time, since the growth terminal is stable, it becomes easy to produce a block copolymer in which both components of the block do not mix. Moreover, since the controllability of the reaction temperature is good, it is easy to suppress side reactions.

A general method of living anionic polymerization using a microreactor will be described with reference to FIG. 1, which is a schematic diagram of the microreactor.
The first monomer and the polymerization initiator for initiating the polymerization are respectively introduced from the tube reactors P1 and P2 (7 and 8 in FIG. 1) into a T-shaped micro mixer M1 (FIG. 1) in 1), and living anion polymerization of the first monomer is performed in the T-shaped micromixer M1 to form a first polymer (step 1).

Next, the obtained first polymer was moved to a T-shaped micromixer M2 (2 in FIG. 1), and the growth end of the obtained polymer was transferred to the tube reactor P3 (FIG. 1) in the mixer M2. The reaction is regulated by trapping with the reaction modifier introduced from 9) (Step 2).
At this time, the number of n in the general formula (3) can be controlled by the type and the amount of the reaction modifier used.

Next, the reaction-controlled first polymer in the T-shaped micromixer M2 is moved to the T-shaped micromixer M3 (3 in FIG. 1), and in the same mixer M3, from the tube reactor P4. Living anion polymerization is continuously performed on the introduced second monomer and the reaction-adjusted first polymer (step 3).

Then, the block copolymer is produced by quenching the reaction with a compound having an active proton such as methanol.

When the polymer (G) represented by the general formula (3) of the present invention is produced in the microreactor, a monomer having an aromatic ring or a heterocycle is used as the first monomer, and an organic compound is used as the initiator. by reacting the lithium initiator, an organic group at one terminal of the polymer block (the polymer block a ² monomers are organolithium initiator residues of the a ¹ having an aromatic ring or a heterocyclic ring of the a ² Are bound).
Next, after adjusting the reactivity of the growth terminal using a reaction modifier, a monomer containing a (meth) acrylate having a reproducible protecting group for the anionic group is reacted as the second monomer to form a polymer block. To get

Thereafter, by reproducing the anionic group by deprotection reaction such as hydrolysis, polymer blocks containing the A ³ i.e. anionic groups are obtained.

Detailed description will be given of a method of regenerating an ester bond of a protective group that is reproducible to the anionic group into an anionic group by deprotection reaction such as hydrolysis.

The hydrolysis reaction of the ester bond proceeds under both acidic and basic conditions, but the conditions differ slightly depending on the group having the ester bond. For example, when the group having an ester bond is a primary alkoxycarbonyl group such as a methoxycarbonyl group or a secondary alkoxycarbonyl group such as an isopropoxycarbonyl group, a carboxyl group is obtained by hydrolysis under basic conditions. be able to. At this time, examples of the basic compound under the basic condition include metal hydroxides such as sodium hydroxide and potassium hydroxide.

When the group having an ester bond is a tertiary alkoxycarbonyl group such as t-butoxycarbonyl group, a carboxyl group can be obtained by hydrolysis under acidic conditions. At this time, examples of the acidic compound under acidic conditions include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; Breasted acids such as trifluoroacetic acid; Lewis acids such as trimethylsilyl triflate. The reaction conditions for hydrolysis under the acidic condition of the t-butoxycarbonyl group are disclosed, for example, in “Chemical Chemistry, Japan, 5th Edition, Experimental Chemistry Lecture 16, Synthesis IV of Organic Compounds”.

Furthermore, as a method for converting a t-butoxycarbonyl group into a carboxyl group, a method using a cation exchange resin in place of the above-mentioned acid can also be mentioned. Examples of the cation exchange resin include resins having an acid group such as a carboxyl group (—COOH) and a sulfo group (—SO ₃ H) in the side chain of the polymer chain. Among these, a cation exchange resin having a sulfo group in the side chain of the resin and exhibiting strong acidity is preferable because the reaction can be accelerated. Examples of commercially available cation exchange resins that can be used in the present invention include strong acid cation exchange resin "Amberlite" manufactured by Organo Corporation. The amount of this cation exchange resin used is preferably in the range of 5 parts by mass to 200 parts by mass, preferably 10 parts by mass, relative to 100 parts by mass of the polymer represented by the general formula (3), since it can effectively hydrolyze. The range of up to 100 parts by mass is more preferable.

Also, when the group having an ester bond is a phenylalkoxycarbonyl group such as a benzyloxycarbonyl group, it can be converted to a carboxyl group by performing a hydrogenation reduction reaction. At this time, as a reaction condition, a phenylalkoxycarbonyl group can be quantitatively regenerated to a carboxyl group by reacting at room temperature in the presence of a palladium catalyst such as palladium acetate using hydrogen gas as a reducing agent.

As described above, since the reaction conditions for conversion into a carboxyl group differ depending on the type of group having an ester bond, for example, t-butyl (meth) acrylate and n-butyl (meth) acrylate are used as raw materials for A ^3. The polymer obtained by copolymerization has a t-butoxycarbonyl group and an n-butoxycarbonyl group. Here, under acidic conditions in which the t-butoxycarbonyl group is hydrolyzed, the n-butoxycarbonyl group does not hydrolyze, and therefore only the t-butoxycarbonyl group can be selectively hydrolyzed and deprotected to a carboxyl group. Becomes Therefore, it is possible to the acid value of the adjustment of the hydrophilic block (A ³⁾ by appropriately selecting a monomer containing a (meth) acrylate having a renewable protecting group an anionic group which is a raw material monomer of A ^3.

In the polymer (G) represented by the general formula (3), the polymer block is not a random copolymer in which the polymer block (A ² ) and the polymer block (A ³ ) are randomly arranged and bonded, and the polymer block is A block copolymer in which a certain length of a block is regularly bound is advantageous in improving the stability of the aqueous pigment dispersion in which the pigment is dispersed in water by the polymer (G). is there. The aqueous pigment dispersion is a raw material used in the production of ink, and is a liquid in which the pigment is dispersed in water at a high concentration using the polymer (G). The molar ratio A ² : A ³ of the polymer block (A ² ) and the polymer block (A ³ ) is preferably in the range of 100: 10 to 100: 500, and A ² :: A ³ = 100: 10 to 100: In order to obtain an ink having a value of 450, for example, it is possible to maintain good ejection stability required when ejecting an ink by an inkjet method, and to manufacture a printed matter having further excellent color developability. Is more preferable.

Further, in the polymer (G) represented by the general formula (3), the number of monomers having an aromatic ring or a heterocycle constituting the polymer block (A ² ) is preferably in the range of 5 to 40, and in the range of 6 to 30. Is more preferable, and the range of 7 to 25 is most preferable. Further, the number of anionic groups constituting the polymer block (A ³ ) is preferably in the range of 3 to 20, more preferably in the range of 4 to 17, and most preferably in the range of 5 to 15.
Configure ^{A 3,} and the number of moles having an aromatic ring or a heterocyclic ring constituting the polymer block ^{(A 2),} the ^{(A 3):} molar ratio ^A 2 of the polymer block ^{(A 2)} and polymer blocks ^{(A 3)} When expressed by the molar ratio of the number of moles of the anionic group, the ratio is preferably 100: 7.5 to 100: 400.

The acid value of the polymer (G) represented by the general formula (3) is preferably 40 mgKOH / g to 400 mgKOH / g, more preferably 40 mgKOH / g to 300 mgKOH / g, and more preferably 40 mgKOH / g to 190 mgKOH / g. That is, for example, in order to obtain an ink capable of maintaining good ejection stability required when ejecting an ink by an inkjet method, and capable of producing a printed matter which is further excellent in terms of scratch resistance and the like. More preferable.

The acid value of the polymer in the present invention is the acid value measured by the same acid value measurement method as the method for measuring the fine particles of the polymer (G).

In the ink, the anionic group of the polymer (G) is preferably neutralized.

As the basic compound for neutralizing the anionic group of the polymer (G), any known and commonly used basic compound can be used, and examples thereof include inorganic basic compounds such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Substances and organic basic compounds such as ammonia, triethylamine and alkanolamine can be used.

The neutralization amount of the polymer (G) present in the aqueous pigment dispersion need not be 100% neutralized with respect to the acid value of the polymer. Specifically, the polymer (G) is preferably neutralized so that the neutralization rate is 20% to 200%, and more preferably 80% to 150%.

As the aqueous medium (C), water alone or a mixed solvent of water and an organic solvent (F) described later can be used.

As the water, specifically, deionized water, ultrafiltered water, reverse osmosis water, distilled water, or other pure water or ultrapure water can be used.

The aqueous medium (C) is preferably used in the range of 1% by mass to 50% by mass with respect to the total amount of the ink, and is preferably used in the range of 10% by mass to 30% by mass when ejecting by an inkjet method. It is particularly preferable in order to obtain an ink capable of producing a clear printed matter, which has high ejection stability required for.

Examples of the organic solvent (F) include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2- Alcohols such as methoxyethanol; Ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Glycols such as polyethylene glycol and polypropylene glycol; butanediol, pentanediol, hexanediol and diols such as diols homologous thereto; lauric acid pro Glycol esters such as len glycol; diethylene glycol monoethyl, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol ether, dipropylene glycol ether, and glycol ethers such as cellosolve including triethylene glycol ether; methanol, ethanol, isopropyl alcohol , Alcohols such as butyl alcohol and pentyl alcohol such as 1-propanol, 2-propanol, 1-butanol and 2-butanol, and alcohols homologous thereto; sulfolane; lactones such as γ-butyrolactone; N- (2- Lactams such as hydroxyethyl) pyrrolidone can be used alone or in combination of two or more.

Further, as the organic solvent (F), in addition to those described above, a water-soluble organic solvent (f1) having a boiling point of 100 ° C. or higher and 200 ° C. or lower and a vapor pressure at 20 ° C. of 0.5 hPa or higher. It is preferable to use (1) to obtain a quick-drying effect of quickly drying on the cloth after the discharged droplets land on the surface of the cloth.

Examples of the water-soluble organic solvent (f1) include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl Ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol Lumpur diethyl ether, dipropylene glycol dimethyl ether, 4-methoxy-4-methyl-2-pentanone, ethyl lactate and the like, may be used in combination with one of the two or more.

Among them, as the water-soluble organic solvent (f1), in order to maintain good dispersion stability of the ink and to suppress deterioration of an ink ejection nozzle of an inkjet device due to the influence of the solvent contained in the ink, for example. , HSP (Hansen solubility parameter) hydrogen bond term δH in the range of 6 to 20 is preferably used.

Specific examples of the water-soluble organic solvent having a hydrogen bond term of HSP within the above range include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol monomethyl ether and ethylene glycol mono. Ethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monopropyl ether are preferable, and 3 is more preferable. -Methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol.

As the organic solvent that can be used in combination with the aqueous medium (C), in addition to the water-soluble organic solvent (f1) described above, or together with the water-soluble organic solvent (f1), propylene glycol (f2) and glycerin, Using in combination with at least one organic solvent (f3) selected from the group consisting of glycerin derivatives, diglycerin and diglycerin derivatives, the effect of quick drying of ink on the cloth and the drying of ink at the ink ejection port It is preferable in terms of achieving both effects of preventing solidification.

Examples of the organic solvent (f3) are represented by glycerin, diglycerin, polyglycerin, diglycerin fatty acid ester, polyoxypropylene (n) polyglyceryl ether represented by the general formula (1), and general formula (2). Polyoxyethylene (n) polyglyceryl ether etc. can be used individually or in combination of 2 or more types.

Among them, the use of glycerin and polyoxypropylene (n) polyglyceryl ether of n = 8 to 15 as the organic solvent (f3) is excellent in the setting property of the printed matter and allows the ink to be dried or coagulated at the ink ejection port. It is particularly preferable for the effect of preventing the above.

In the general formulas (1) and (2), m, n, o and p each independently represent an integer of 1 to 10.

The organic solvent (F) is preferably used in the range of 1% by mass to 30% by mass with respect to the total amount of the ink, and is preferably used in the range of 5% by mass to 25% by mass in order to set the printed matter. It is excellent and is particularly preferable in that it has the effect of preventing the ink from drying or coagulating at the ink ejection port.

The water-soluble organic solvent (f1), propylene glycol (f2), and organic solvent (f3) have a mass ratio [water-soluble solvent (f1) / propylene glycol (f2)] of 1 / 25-1 / 1. It is preferable to use in the range of 1/20, and it is particularly preferable to use in the range of 1/20 to 1/1 because the set property of the printed matter is excellent and the effect of preventing the ink from drying or coagulating at the ink discharge port is exhibited. .

The mass ratio [propylene glycol (f2) / organic solvent (f3)] of the water-soluble organic solvent (f1), propylene glycol (f2) and the organic solvent (f3) is 1/4 to 8 /. It is preferable to use it in the range of 1, and it is particularly preferable to use it in the range of 1/2 to 5/1 because it has excellent settability for printed matter and prevents the ink from drying or coagulating at the ink discharge port. preferable.

In addition to the above-mentioned components, the ink of the present invention may further contain a surfactant (E), a saccharide, an antiseptic, a viscosity adjusting agent, a pH adjusting agent, a chelating agent, an antioxidant, an ultraviolet absorber, and the like, if necessary. It is possible to use those containing the additive of.

The surfactant (E) can be used to improve the leveling property of the ink by lowering the surface tension of the ink. Furthermore, the surface-active agent (E) can prevent streaks on printed matter by allowing the ink ejected from the ejection ports of the inkjet head to satisfactorily spread on the surface after landing on the cloth.

As the surfactant (E), various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used, and anionic surfactants and nonionic surfactants can be used. Preference is given to using surfactants.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, higher fatty acid ester sulfate ester salt, higher fatty acid ester sulfonate, and higher alcohol. Sulfate ester salts and sulfonates of ethers, higher alkylsulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates and the like. As specific examples of these, dodecylbenzene sulfonate, isopropyl naphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenyl sulfonate, dibutylphenylphenol disulfonate Or the like can be mentioned sulfonic acid salt.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol , Polyethylene glycol polypropylene glycol block copolymer, etc. , Of these, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, Fatty acid alkylolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymer are preferred. Among them, acetylene glycol and an oxyethylene adduct of acetylene glycol are more preferable because they can reduce the contact angle of ink droplets with respect to the recording medium and can obtain good printed matter.

Other surfactants include silicone-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Agents; biosurfactants such as spiculisporic acid, rhamnolipid, and lysolecithin can also be used.

As the surfactant (E), one having an HLB in the range of 4 to 20 is used in order to stably maintain the state in which the surfactant (E) is dissolved in an ink containing water as a main solvent. Preferably.

The surfactant (E) is preferably used in the range of 0.001% by mass to 2% by mass, and is used in the range of 0.001% by mass to 1.5% by mass, based on the total amount of the ink. It is more preferable to use it, and it is preferable to use it in the range of 0.5 to 1.5% by mass. The inkjet ink containing the surfactant (E) in the above range has good wettability of discharged droplets on the surface of the cloth, has sufficient wet spread on the cloth, and has an effect of preventing streaks on printed matter. It is preferable for playing. Further, the ink containing the surfactant (E) in the above range has the effect of improving the wettability to the cloth and the leveling property.

Examples of the saccharides include monosaccharides and polysaccharides, glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, and the like. Alginic acid and its salts, cyclodextrins, and celluloses can be used.

Examples of the preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (available from Arch Chemicals). Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, Proxel DL) and the like.

Specific examples of the viscosity modifier include mainly water-soluble natural or synthetic polymers such as carboxymethyl cellulose, 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 the chelating agent include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, and uramildiacetic acid. , 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid and salts thereof (including hydrates) and the like.

As the antioxidant or ultraviolet absorber, alohanates, alohanates such as methylallohanate, biuret, dimethylbiuret, biurets such as tetramethylbiuret, L-ascorbic acid and salts thereof, etc., Tinuvin 328 manufactured by Ciba Geigy, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, and lanthanide oxides.

(Ink manufacturing method)
In the ink of the present invention, when the coloring material (B) is a pigment, an aqueous pigment dispersion containing a high concentration of the pigment is produced, and the aqueous medium (C) and the binder resin (A) or the surface active agent are used. It can be produced by mixing the agent (E) and, if necessary, other additives.

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 a mixture containing a dispersion resin and water and then dispersing the pigment in the mixture using a stirring and dispersing device.
(2) The pigment and the dispersion resin are kneaded by using a kneader such as a two-roll mill or a mixer, and the resulting kneaded product is added with water and, if necessary, an organic solvent miscible with water, and a stirring and dispersing device is added. A method for preparing an aqueous pigment dispersion by using.
(3) A pigment is added to a solution obtained by dissolving a dispersion resin in an organic solvent having compatibility with water such as methyl ethyl ketone and tetrahydrofuran, and then the pigment is dispersed in the organic solution by using a stirring dispersion device. And then phase inversion emulsification using an aqueous medium, and then the organic solvent is distilled off 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, a planetary mixer, and a butterfly mixer.

As the stirring and dispersing device, for example, 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 dispermat, an SC mill, a nanomizer and the like can be used alone or in combination of two or more kinds. .

As the aqueous pigment dispersion, it is preferable to use a pigment containing 5% by mass to 60% by mass of the total amount of the aqueous pigment dispersion, because a printed matter with high image density can be formed and dispersion stability is excellent. It is preferable in order to obtain the above ink, and it is more preferable to use an aqueous pigment dispersion which is 10% by mass to 50% by mass.

Further, since coarse particles contained in the aqueous pigment dispersion cause deterioration of image characteristics, use an aqueous pigment dispersion from which coarse particles have been removed by centrifugation or filtration before and after producing the ink. Is preferred.

When manufacturing the above-mentioned aqueous pigment dispersion, a post-treatment may be carried out after an impurity removal step by ion exchange treatment or ultra-treatment after the dispersion step. 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 the dispersion composition). , Resin that is not adsorbed on the organic pigment, mixed foreign matter, etc.) can be removed. A known ion exchange resin is used for the ion exchange treatment. For the ultra treatment, a known ultrafiltration membrane is used, and either a normal type or a double capacity type may be used.

For the ink of the present invention, the pigment concentration is preferably 1% by mass to 20% by mass in order to obtain a sufficient image density and to secure good dispersion stability of the pigment in the ink.

The pH of the ink is preferable in order to improve storage stability and ejection stability of the ink and to improve wettability and spread when printed on a fabric that is easily absorbable or difficult to absorb ink, print density, and water fastness. Is 7.0 or more, more preferably 7.5 or more, and even more preferably 8.0 or more. The upper limit of the pH of the ink suppresses deterioration of members (for example, an ink ejection port, an ink flow path, etc.) that configure the ink application or ejection device, and reduces the influence when the ink adheres to the skin. In addition, it is preferably 11.0 or less, more preferably 10.0 or less, still more preferably 9.5 or less.

The ink is ejected onto the surface of the cloth exclusively by an inkjet recording method. Further, since the ink is used for printing on cloth, it can be suitably used as a so-called textile printing agent.
Generally, a cloth means a woven fabric made by weaving yarns made of fibers such as cotton alternately in the longitudinal direction and the transverse direction. The ink of the present invention is suitable not only for cloth in the general sense, but also for media composed of fibers such as non-woven fabric and knitted fabric. As the material, a cloth made of any natural fiber or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, rayon or the like, or a cloth obtained by mixing these can be used.

The printed matter obtained by the method for producing a printed matter according to the present invention has excellent added quality and excellent waterfastness, and thus is used for textiles for home textiles such as clothes, curtains, covers and sheets. be able to.

Hereinafter, the present invention will be described in more detail with reference to examples.

<Synthesis Example of Dispersion 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. 1, and living anion polymerization was performed to obtain a polymer.

Next, the polymer obtained in the above step was moved to the T-shaped micromixer M2 through the tube reactor R1 shown in FIG. 1, and the growth end of the polymer was introduced into the reaction regulator (α- Trapped with methyl styrene (α-MeSt).

Then, a tert-butyl methacrylate solution prepared by previously dissolving tert-butyl methacrylate in tetrahydrofuran was introduced from the tube reactor P4 shown in FIG. 1 into the T-shaped micromixer M3, and the trapped polymer moved through the tube reactor R2. , Continuous living anionic polymerization reaction was performed. Then, a block copolymer (PA-1) composition was produced 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 immersing the entire microreactor shown in FIG. 1 in a constant temperature bath.

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

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

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

(Measurement method of weight average molecular weight (Mw))
The measurement was carried out by the gel permeation chromatography (GPC) method under 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 and used.

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

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

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

<Production Example 1> Method for producing 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 parts of the dispersion resin (P-1) are prepared. Parts by mass, 150 parts by mass of triethylene glycol, and 11.5 parts by mass of a 34% by mass aqueous potassium hydroxide solution were charged into a 1.0 L intensive mixer (Nippon Eirich Co., Ltd.), a rotor peripheral speed was 2.94 m / s, and a pan was used. Kneading was performed for 60 minutes at a peripheral speed of 1 m / s.

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

<Example 1> Preparation of aqueous ink and printed matter 30 parts by mass of the aqueous pigment dispersion (A1), 7 parts by mass of a urethane resin composition (nonvolatile content 23% by mass) described below as a binder resin, Surfynol 440 (manufactured by EVONIK). , Acetylene-based surfactant) 1 part by mass, glycerin 25 parts by mass, triethylene glycol 1 part by mass, 3-methyl-1,5-pentanediol 1 part by mass, as a preservative, ACTICIDE B-20 (So Japan) A water-based ink was obtained by mixing 0.2 part by mass of Co., Ltd. and 34.8 parts by mass of ion-exchanged water. The aqueous ink had a viscosity at 25 ° C. of 10 mPa · s and a surface tension of 34 mN / m.

The ink jet head of a piezo type ink jet printer is filled with the water-based ink obtained in the example, and the normal line assumed to the surface (x) intersects with the cloth from the surface (x) having the ink discharge port of the ink jet head. The distance (gap) to the position (y) was set to 3 mm. As the cloth, cotton broad (manufactured by Shikiso Co., Ltd.) was used.

After wiping the nozzle surface of the inkjet head, a 100% solid image is printed on the cloth at a driving frequency of 10 kHz, followed by drying at 100 ° C. for 1 minute and then heating at 150 ° C. for 5 minutes. A printed matter was obtained by performing the treatment.

<Method for producing binder resin>
500 parts by mass of polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-replaced container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 2 , 2-Dimethylolpropionic acid (37.7 parts by mass) and methyl ethyl ketone (420 parts by mass) were added and mixed uniformly. Next, 92.4 parts by mass of tolylene diisocyanate was added, and then 0.1 part by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 7 hours to give a polyurethane (PUD-1) (acid having a weight average molecular weight of 40,000). An organic solvent solution having a valence of 35 mg KOH / g) was obtained. Thereafter, the mixture was cooled to 50 ° C., 29.8 parts by mass of triethylamine and 2069 parts by mass of water were added, methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water was added to adjust the concentration. A urethane resin composition having a nonvolatile content of 23 mass% in which the urethane resin (PUD-1) was dispersed in an aqueous medium was obtained.

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

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

(Method of measuring acid value)
Based on JIS test method K0070-1992, it was determined under the above-mentioned conditions.

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

The viscosity and surface tension of the water-based ink were measured by the following methods.

The viscosity of the ink was measured under the following conditions using a cone-plate type (cone-plate type) rotary viscometer corresponding to the E-type viscometer.
Measuring device: TVE-25 type viscometer (manufactured by TVE-25 L)
Calibration standard solution: JS20
Measurement temperature: 32 ° C
Rotation speed: 10-100 rpm
Injection volume: 1200 μL
The static surface tension of the ink was measured under the following conditions using an automatic surface tension meter to which the Wilhelmi method was applied.
Measuring device: Automatic surface tensiometer (Kyowa Interface Science Co., Ltd., CBVP-Z type)
Measurement temperature: 25 ° C
Stylus: platinum plate

<Examples 2 to 4> Preparation of aqueous ink A printed matter was obtained in the same manner as in Example 1 except that the droplet size of the ink was changed to the value shown in Table 1.

[Evaluation of ink density]
The ink density (OD value) of the printed material obtained by the above method was measured using X-Rite (spectrodensitometer / colorimeter manufactured by X-Rite Co., Ltd.) to evaluate the ink density on the cloth.

[Evaluation of print quality]
The printed matter obtained by the above method was read by a scanner, the portion not coated with the ink was calculated by the image analysis software "ImageJ", and the image quality was evaluated.

◯: The proportion of the printed matter not coated with ink is less than 5%. Δ: The proportion of the printed matter not coated with ink is 5% or more and less than 10%. X: The proportion of the printed matter not coated with ink. Is 10% or more

[Evaluation of wash resistance]
The printed matter obtained by the above method was tested according to JIS L 0844: 2005, A-2 method, and then, according to the criterion of the visual sense method using a gray scale for discoloration of JIS L 0801: 2004. The grade was judged according to grades 1-5. It should be noted that the grade was evaluated such that the 1st grade was the most discolored and the closer to the 5th grade, the less discolored.

[Evaluation of abrasion resistance]
The printed matter obtained by the above method is subjected to dry and wet tests using a Gakushin-type friction fastness tester according to JIS L 0849: 2004, and then discoloration of JIS L 0801: 2004. Grades were evaluated according to grade 1 to grade 5 according to the criteria of the visual sense method using a gray scale for use. As for the grade, the 1st grade is the most discolored, and the closer to the 5th grade, the less discolored.

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

Claims (3)

1. The method comprises a printing step of obtaining a printed matter by printing ink on a cloth by an inkjet recording method, and in the printing step, the shortest distance between the ink ejection port of the inkjet head and the cloth is 2 mm or more, and the ink is ejected from the inkjet head. A method for producing a printed matter, wherein the size of each ink droplet is 10 to 50 pl.
2. The method for producing a printed matter according to claim 1, wherein the ink contains the binder resin (A) in an amount of 1 to 15 mass% with respect to the total amount of the ink.
3. The method for producing a printed matter according to claim 1, wherein the ink has a viscosity of 20 mPa · s or less and a surface tension of 20 mN / m to 40 mN / m.

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