JP6886601B2 - Printed matter manufacturing method - Google Patents

Description

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 the inkjet recording method, digitization by inkjet is progressing from the conventional analog method such as screen printing. Just as printers for plain paper and inkjet paper are widely used in ordinary households, the applications are expanding for various base materials for industrial use, and a wide variety of products such as coated paper, cardboard, and film are available. Development is expanding with inkjet printers. Also, in the printing of printing images such as letters, pictures, and patterns on textile base materials such as cotton knits and non-woven fabrics used for fabrics and T-shirts, clothes, curtains, covers, etc. are printed using an inkjet printer. Methods for manufacturing textile products for home textiles such as sheets are being studied. In order to apply the inkjet recording method to these fabrics, it is necessary to achieve both the print image quality and the performance such as washing resistance and abrasion resistance of the printed textile. However, when the distance between the inkjet head and the fabric, that is, the so-called gap, becomes wide, the ejected ink droplets tend to be bent in flight and the landing position is displaced, which causes a problem that a predetermined image quality cannot be obtained.

Therefore, there is a demand for an ink having a small gap in the landing position even when the gap is wide, and an ink having good washing resistance and abrasion resistance for the printed cloth after printing.

When printing on the surface of the cloth by the inkjet recording method, 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 occurs. Therefore, in order to prevent the 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 inkjet head lands on the surface of the fabric becomes long, so that the flying bending of the ink droplets that may occur before the landslide occurs. The landing position is likely to shift excessively. Further, as the distance becomes longer, the ejection speed due to air resistance also decreases, so that the spread of the ink on the surface of the cloth becomes insufficient, and there is a case that a problem in image quality such as streaks appearing in the printed matter may occur.

Japanese Unexamined Patent Publication No. 2011-12226

The problem to be solved by the present invention is that, 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 having excellent image quality without streaks, and it is washed or scratched. 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 discoloration, color transfer, peeling, etc. even in such a case.

The present invention includes 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 inkjet. The present invention relates to a method for producing a printed matter, wherein the size of one 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 fabric and the inkjet head is long, it is possible to produce a printed matter having desired image quality without printing streaks. It can be suitably used for manufacturing textile products for home textiles such as sheets.

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

The method for producing a printed matter of the present invention includes 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 one ink droplet ejected from the inkjet head is in the range of 10 to 50 pl.

The shortest distance is the distance from the surface (x) having the ink ejection port of the inkjet head to the position (y) where the perpendicular line of the surface (x) (the perpendicular line assumed with respect to the surface (x)) and the fabric intersect. It may be (gap).

In the inkjet recording method applied in the method for producing 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 the surface (recording surface) of the cloth from coming into contact with the ink ejection port even if the fabric has large fluffing or unevenness, and damages the ink ejection port or the ink. In addition to effectively preventing ink ejection defects caused by the deterioration of the water-repellent function that the ejection port often has, even when the distance between the surface of the fabric and the inkjet head is long, printed matter without streaks can be produced. 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, and particularly preferably 5 mm or less.

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

As the ink, an ink having a lower limit of viscosity at 30 ° C. of preferably 4 mPa · s or more can be used, more preferably 6 mPa · s or more, still more 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 even more preferably 12 mPa · s. The following can be used.

In the ink having the viscosity in the above range, since the droplets ejected from the inkjet head have a sufficient volume, the vertical line of the surface (x) and the cloth are formed 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, the deviation of the landing position on the cloth caused by the flight bending can be apparently reduced, and the occurrence of streaks on the printed matter can be effectively prevented.

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

The viscosity of the ink was measured under the following conditions using a conical plate type (cone plate type) 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, as the ink, an ink having a lower limit of surface tension at 25 ° C. of preferably 20 mN / m or more can be used, more preferably 25 mN / m or more, still more 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.

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

The surface tension of the ink refers to a value measured under the following conditions using an automatic tensiometer to which the Wilhelmi method is applied. According to the Wilhelmi 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 tensiometer (CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.)
Measurement temperature: 25 ° C
Meter: Platinum plate

As the ink, any ink having the 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. Can be done. Among them, as the ink, it is preferable to use an ink 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 an ink in which the binder resin (A), the coloring material (B) and the like are dissolved or dispersed in an aqueous medium (C) which is a solvent.

The binder resin (A) is for fixing the pigment on the recording medium. Especially in the case of printing on a cloth, if an ink having a high content of the binder resin (A) is used, the washing resistance and abrasion resistance (wet and dry type) of the printed matter are improved, but the texture of the cloth becomes 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, and the lower limit of 1% by mass or more is preferably used in the range of 20% by mass or less with respect to the total mass of the ink. Preferably, 5% by mass or more is more preferable for obtaining a printed matter having excellent washing resistance and abrasion resistance.

As described above, the binder resin (A) is for fixing a coloring material (B) such as a pigment on the cloth. When a binder resin having a glass transition temperature exceeding room temperature is used, the texture of the fabric tends to be slightly hardened. Therefore, as the binder resin (A), particularly one having a glass transition temperature of 0 ° C. or less maintains good texture and washing resistance even when ink or printed matter is used in a low temperature area. It is preferable to do so.

The ratio of the binder resin (A) to the color material (B) may be a ratio within the range normally used for 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 for obtaining a printed matter having even better abrasion resistance. Further, as the binder resin (A), in order to obtain a printed matter having even more excellent abrasion resistance, it is preferable to use a binder resin having a large weight average molecular weight, which imparts even more excellent ejection properties. 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 resin, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer, and vinyl acetate-acrylic acid ester. Acrylic copolymers such as polymers, acrylic acid-alkyl ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-alkyl ester copolymers, styrene Styrene-acrylic acid resins such as -α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-alkyl ester copolymer; styrene-maleic acid; styrene-maleic anhydride; vinylnaphthalene -Acrylic 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 Vinyl acetate-based copolymers such as polymers and vinyl acetate-acrylic acid copolymers and salts thereof can be used.

Among them, it is preferable to use urethane resin or acrylic resin as the binder resin in order to easily obtain it and to improve the abrasion resistance of the printed matter, and in particular, the washing resistance of the printed matter on the cloth (washing fastness). Degree) and abrasion resistance (dry friction fastness and wet friction fastness) are preferable for further improvement.

The urethane resin includes one or more polyols selected from the group consisting of polyether polyols, polyester polyols and polycarbonate polyols, and anionic groups, cationic groups, polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups. 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 5000 to 200,000, more preferably 2000 to 150,000, in order to further improve the friction 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, and neopentyl glycol. Glycerin, trimethylol ethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, femmellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyfutaric acid, 1,2,3-propane A compound having two or more active hydrogen groups such as trithiol and an addition polymerization of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclophenylene, or the cyclic ether compound. Can be mentioned as a ring-opened polymer using a cation catalyst, a protonic acid, a Lewis acid, or the like as a catalyst.

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

Examples of the dicarboxylic acid used as a raw material for the polyester polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 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 used as a raw material for the polyester polyol include p-hydroxybenzoic acid and p- (2-hydroxyethoxy) benzoic acid.

As the polycarbonate polyol, for example, 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 and the like 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, and 1 , 3-Butandiol, 1,2-Butandiol, 2,3-Butandiol, 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 -Relatively low molecular weight dihydroxy compounds such as -cyclohexanedimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4'-biphenol, and polyether polyols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol. Alternatively, polyester polyols such as polyhexamethylene adipate, 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 used for producing the polycarbonate-based urethane resin and the polyisocyanate.

In addition, the urethane resin has a hydrophilic group in order to impart dispersion stability in the ink.

As the hydrophilic group, an anionic group, a cationic group, or a nonionic group can be generally used, but it is preferable to use an anionic group or a cationic group.

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

Examples of the basic compound that can be used for neutralizing the carboxyl group and the sulfonic acid group as the anionic group include organic amines such as ammonia, triethylamine, pyridine and morpholine, alkanolamines such as monoethanolamine, and Na. Examples thereof include metal base compounds containing K, Li, Ca and the like, and among them, it is preferable to select an organic amine having a boiling point of 100 ° C. or lower in order to reduce the residue on the dry film.

Further, as the cationic group, for example, a tertiary amino group or the like can be used. As the acid that can be used to neutralize a part or all of the tertiary amino group, formic acid, acetic acid and the like can be used, for example. Further, as the quaternizing agent that can be used when partially or all of the tertiary amino group is quaternized, for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.

The nonionic group includes, for example, a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among them, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

The presence of 0.5% by mass to 30% by mass of the hydrophilic group with respect to the entire urethane resin imparts even better water dispersibility, and may be in the range of 1% by mass to 20% by mass. More preferred.

Further, in the ink of the present invention, a cross-linking agent described later can be used for the purpose of further improving the friction resistance. When the cross-linking agent is used, it is preferable to use the urethane resin having a functional group capable of cross-linking 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 groups and the like contribute to the water dispersion stability of the urethane resin in an aqueous medium, and when they undergo a cross-linking reaction, they also act as the functional groups and can partially carry out a cross-linking reaction of the cross-linking 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 to improve the above. 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 a chain extender, if necessary.

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

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, and 3,3'-. Diamines such as dimethyl-4,4'-dicyclohexamethylenediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; dihydrazide succinate, dihydrazide adipate, dihydrazide glutarate, sebacic acid Dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionate hydrazide, 3-semicarbazid-propyl-carbazic acid ester, semicarbazid-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane can be used and ethylenediamine. It is preferable to use.

Examples of the other active hydrogen-containing compound include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and neo. Glycos 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 Etc., and water, etc. can be used.

In the chain extender, for example, the equivalent of the amino group and the active hydrogen atom-containing group of the chain extender is the equivalent of the isocyanate group of the urethane prepolymer obtained by reacting the polyol with 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 reacting the polyol with polyisocyanate or after the reaction. Further, the chain extender can also be used when the urethane resin obtained above is dispersed in an aqueous medium to make it aqueous.

Examples of polyols other than the above include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 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 their alkylene oxide adducts, glycerin, trimethylolethane, trimethylolpropane, sorbitol, pentaerythritol and other relatively low molecular weight polyols. These polyols can be used alone or in combination of two or more.

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

The acrylic resin that can be used for 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" refers to methacrylic acid or acrylic acid, "(meth) acrylate" refers to methacrylate or acrylate, and "(meth) acryloyl" refers to methacrylic acid or acryloyl. Point to.

Examples of vinyl monomers that can be copolymerized with (meth) acrylates and (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t. -Alkyl (meth) acrylates such as butyl (meth) acrylates, isopropyl (meth) acrylates and isobutyl (meth) acrylates; aromatic (meth) acrylates such as benzyl (meth) acrylates; 2-hydrodoxyethyl (meth) acrylates. , 2-hydroxypropyl (meth) acrylate and other hydroxyl group-containing monomers; methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate and other alkyl polyalkylene glycol mono (meth) acrylate; perfluoroalkyl ethyl (meth) acrylate ) Fluorine-based (meth) acrylates such as acrylates; styrene, styrene derivatives (p-dimethylsilylstyrene, (p-vinylphenyl) methylsulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyldimethylsiloxystyrene) , O-Methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, etc.), vinylnaphthalene, vinylanthracene, aromatic vinyl compounds such as 1,1-diphenylethylene; glycidyl (meth) acrylate, Epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylpropantri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diacryloxy Propane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylatetricyclodecanyl (meth) (Meta) acrylate compounds such as acrylate, tris (acryloxyethyl) isocyanurate, urethane (meth) acrylate; alkylamino such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate (Meta) acrylate having a group; Vinyl pyridine compound such as 2-vinylpyridine, 4-vinylpyridine, naphthylvinylpyridine; 1 , 3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, conjugated diene such as 1,3-cyclohexadiene, etc. Can be 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-mentioned monomer in order to improve the texture of the 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 and the like can be used.

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

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

The dispersion form of the acrylic resin in water is not particularly limited, and examples thereof include an emulsion forcibly emulsified with an emulsifier, a dispersion having a nonionic group or a neutralized ionic group in the resin, and the like. In particular, 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 compound as those exemplified as those that can be used for neutralizing the carboxyl group and the like possessed by the urethane resin can be used.

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

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

Further, as the pigment, either an acid-treated pigment or an acid-treated pigment can be used, and either a dry powder or a wet cake-like pigment 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 (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofuralon pigments, etc.), lake pigments (for example, basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

As a specific example of the pigment, if it is a pigment used for black ink, No. 1 manufactured by Mitsubishi Chemical Corporation. 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., Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Colombia, Regal 400R, Regal 330R, Regal 660 manufactured by Cabot Corporation, etc. 700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, etc. are Color Black FW1, FW2, FW2V, FW18, FW200, ntS150, S150 Carbon blacks such as U, V, 1400U, Special Black 6, 5, 4, 4, A, NIPEX150, NIPEX160, NIPEX170, and NIPEX180 can be used.

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 can be mentioned.

Specific examples of pigments used in magenta ink include C.I. I. Pigment Violet 19, C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209 and their pigments. A mixture or solid solution of at least two or more pigments selected from the above can be mentioned.

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. One or more selected from the group consisting of Pigment Red 17, 49: 2, 112, 149, 150, 177, 178, 179, 188, 254, 255 and 264 are preferably used.

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

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

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

Specific examples of pigments that can be used in white ink include silicas such as sulfates of alkaline earth metals, carbonates, fine silicic acid, synthetic silicates, calcium silicate, alumina, and alumina hydrate. 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.

In order for the pigment to be stably present in the ink, it is preferable to take measures to disperse the pigment well in the aqueous medium (C).

As the means, for example, (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) on the surface of the pigment. Examples thereof include a method of dispersing and / or dissolving a self-dispersing pigment in which the salt) is directly or indirectly bonded via an alkyl group, an alkyl ether group, an aryl group or the like in an aqueous medium (C).

As the self-dispersion pigment, for example, a pigment obtained by subjecting the pigment to a physical treatment or a chemical treatment and binding (grafting) an active species having a dispersibility-imparting group or a dispersibility-imparting group to the surface of the pigment is used. be able to. The self-dispersing pigment is, for example, vacuum plasma treatment, oxidation treatment with hypohalous acid and / or hypohalite, 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 a carboxyl group is bonded via a phenyl group by binding p-aminobenzoic acid to the surface of the pigment.

Since the water-based ink containing the self-dispersing pigment does not need to contain the pigment dispersant, there is almost no foaming or the like caused by the pigment dispersant, and it is easy to prepare an ink having excellent ejection stability. In addition, the water-based ink containing the self-dispersing pigment is easy to handle, and since a large increase in viscosity due to the pigment dispersant is suppressed, it is possible to contain a larger amount of pigment, and a printed matter having a high printing density can be produced. Can be used for.

As the self-dispersing pigment, a commercially available product can also be used, and such a commercially available product includes Microjet CW-1 (trade name; manufactured by Orient Chemical Industries Co., Ltd.), CAB-O-JET200, Examples include CAB-O-JET300 (trade name; manufactured by Cabot Corporation).

In the present invention, if an attempt is made to excessively change the composition of the ink in order to prevent deterioration of image quality such as streaks, the print density and washing resistance of the printed matter may tend to decrease. The color material (B) prevents the occurrence of the streaks, maintains the excellent dispersion stability of the color material (B), and improves the print density and washing resistance of the printed matter. It is preferable to use in the range of 1% by mass to 20% by mass, and more preferably in the range of 2% by mass to 10% by mass with respect to the total amount of.

(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, and styrene-methacrylic acid. Styrene-acrylic resin such as -acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer A coalescence, a styrene-maleic anhydride copolymer, an aqueous resin of a vinylnaphthalene-acrylic acid copolymer, and a salt of the aqueous resin can be used. Examples of the pigment dispersant include Ajinomoto Fine-Techno Co., Ltd.'s Ajispar PB series, Big Chemie Japan's Co., Ltd. Disperbyk series, BASF's EFKA series, Japan Lubrizol Co., Ltd.'s SOLPERSE series, and Evonik's. TEGO series and the like can be used.

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

As the polymer (G), a polymer having an anionic group can be used, among which the polymer (G) has a solubility in water of 0.1 g / 100 ml or less and is made of a 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 can form 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 having a mesh size of 250 μm and 90 μm is sealed in a bag processed with a 400 mesh wire mesh, immersed in 50 ml of water, and immersed at 25 ° C. The mixture was gently stirred for 24 hours at a temperature. After soaking for 24 hours, a 400-mesh wire mesh containing the polymer (E) was dried in a dryer set at 110 ° C. for 2 hours. The change in weight of the 400 mesh wire mesh containing 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 fine particles are formed in water when the neutralization rate by the basic compound of the anionic group is set to 100% was determined as follows.
(1) The acid value of the polymer (G) is measured in advance by an acid value measuring method based on the JIS test method K0070-1992. Specifically, 0.5 g of the polymer (G) is dissolved in tetrahydrofuran and titrated with a 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 that only neutralizes the obtained acid value by 100% is added to achieve 100% neutralization.
(3) The 100% neutralized liquid was irradiated with ultrasonic waves in an ultrasonic cleaner (SND Ultrasonic Cleaner US-102, 38 kHz self-excited oscillation) for 2 hours at a temperature of 25 ° C. Then leave it at room temperature for 24 hours.

After leaving it for 24 hours, the sample liquid sampled at a depth of 2 cm from the liquid surface is used as a dynamic light scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., dynamic light scattering particle size measuring device "Micro". Using a track particle size distribution meter UPA-ST150 "), it is confirmed whether or not fine particles are present by determining whether or not light scattering information due to 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 size of the fine particles is preferably in the range of 5 nm to 1000 nm, preferably in the range of 7 nm to 700 nm. It is more preferable, and it is most preferably in the range of 10 nm to 500 nm. Further, the narrower 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, an ink having better dispersion stability than the conventional one can be obtained. As for the particle size and particle size distribution, the dynamic light scattering type particle size distribution measuring device (dynamic light scattering type particle size measuring device "Microtrack particle size distribution meter UPA" manufactured by Nikkiso Co., Ltd.) is the same as the method for measuring the fine particles. -ST150 ") was used for measurement.

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 the JIS test method K0070-1992. Specifically, it was obtained by dissolving 0.5 g of a sample in tetrahydrofuran and titrating with a 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.

The polymer (G) preferably has a number average molecular weight in the range of 1000 to 6000, more preferably 1300 to 5000, and preferably 1500 to 4500 as a pigment in the aqueous medium (C). It is more preferable to obtain an ink having good dispersion stability of the color material (B), which can effectively suppress the aggregation of the color material (B) such as the above.

The number average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography), and specifically, a value measured under the following conditions.

(Measurement method of number average molecular weight (Mn))
It was measured 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 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel 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 amount: 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)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

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, which is close to the surface tension of water. It is particularly preferable to use the one that is. The surface tension of the polymer solution was 100% neutralized by adding 1 g of the polymer (G) to water and then adding a 0.1 mol / L potassium hydroxide aqueous solution that only neutralized the obtained acid value by 100%. It is a value measured about.

As the polymer (G), a polymer that is insoluble or sparingly soluble in water in an unneutral state and forms fine particles in a 100% neutralized state can be used, and is a hydrophilic group. 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.

Examples of such a polymer include a block polymer having a polymer block having a hydrophobic group and a polymer block having an anionic group. In the polymer (G), the number of anionic groups and the solubility in water are not necessarily specified by the acid value or the number of anionic groups at the time of polymer design, for example, a polymer having the same acid value. Even if they are present, those having a low molecular weight tend to have a high solubility in water, and those having a high molecular weight tend to have a low solubility in water. From this, in the present invention, the polymer (G) is specified by its 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 is particularly a block polymer. Is preferable. The polymer may be a branched polymer, but is preferably a linear polymer.

Further, the polymer (G) is preferably a vinyl polymer from the viewpoint of design freedom, and as a method for producing a vinyl polymer having the desired molecular weight and solubility characteristics in the present invention, living radical polymerization and living cationic polymerization are used. , It is preferable to produce 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 method for producing such a vinyl polymer, living radical polymerization and living anionic polymerization are used. Is preferable, and living anionic polymerization is preferable from the viewpoint of the molecular weight of the block polymer and the more precise design of each segment.

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 organic lithium initiator residue, A ² represents a polymer block having a hydrophobic group, A ³ represents a polymer block containing an anionic group, and n represents 1 to 5. Represents an integer of, and B represents an aromatic group or an alkyl group.

In general formula (3), A ¹ represents an organolithium initiator residue. Specific examples of organolithium initiators include methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.), pentyllithium, hexyllithium, etc. Alkyllithium such as methoxymethyllithium and etoshikimethyllithium; phenylalkylenelithium such as benzyllithium, α-methylstyryllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium and phenylethyllithium Alkenyl lithium such as vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium; alkynyl lithium such as ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium; aryl lithium such as phenyllithium, naphthyllithium; 2-thienyl Heterocyclic lithium such as lithium, 4-pyridyllithium and 2-quinolyllithium; alkyllithium-magnesium complexes such as tri (n-butyl) magnesium lithium and trimethylmagnesium lithium can be mentioned.

In the organolithium initiator, the bond between the organic group and lithium is cleaved to generate an active terminal on the organic group side, and polymerization is started from there. Therefore, an organic group derived from organolithium is bonded to the terminal of the obtained polymer. In the present invention, the organic lithium-derived organic group 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 heterocycle is specifically obtained by homopolymerizing or copolymerizing a monomer having an aromatic ring such as a styrene-based monomer or a monomer having a heterocycle such as a vinylpyridine monomer. It is a polymer block of a homopolymer or a copolymer obtained in the 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, and the like. 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, etc.

Examples of the monomer having a heterocycle include vinylpyridine-based monomers such as 2-vinylpyridine and 4-vinylpyridine. These monomers can 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 is another object to provide a described above moderate solubility, there is a purpose of imparting dispersion stability in water when a pigment dispersion.
Anionic groups in the polymer block A ^3, for example, carboxyl group, sulfonic acid group or phosphoric acid group. Of these, the carboxyl group is preferable because of its preparation and the abundance of monomer varieties that are easily available. Further, the two carboxyl groups may be an acid anhydride group obtained by intramolecular or intermolecular dehydration condensation.

Method for introducing anionic groups of the A ³ is not particularly limited, for example, the case the anionic group is a carboxyl group, (meth) homopolymer obtained by copolymerizing a homopolymer or other monomers acrylic acid or It may be a polymer block (PB1) of a copolymer, or a homozygous obtained by homopolymerizing or copolymerizing a (meth) acrylate having a regenerative protecting group as an anionic group by deprotection. The polymer or copolymer may be a polymer block (PB2) in which some or all of the protecting groups reproducible to the anionic group are regenerated into an anionic group.

Incidentally, the A polymer block used in A ³ (meth) acrylic acid represents the general term for acrylic acid and methacrylic acid, and (meth) acrylate represents the general 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 acrylate, n-hexyl (meth) acrylate, n-octyl acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate, n (meth) acrylate -Tridecyl, n-stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, (meth) acrylate Isobornyl, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfurfryl (meth) acrylate, (meth) acrylic 2-methoxyethyl acid, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate , (Meta) pentafluoropropyl acrylate, (meth) octafluoropentyl acrylate, (meth) pentadecafluorooctyl acrylate, (meth) heptadecafluorodecyl acrylate, N, N-dimethyl (meth) acrylamide, ( Meta) Acryloylmorpholine, (Meta) 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, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol (meth) acrylate, lauroxypolyethyleneglyco Contains polyalkylene oxide groups such as ole (meth) acrylate, stearoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate. Examples include (meth) acrylate. These monomers can be used alone or in admixture of two or more.

In the living anionic polymerization method, when the monomer used is a monomer having a group having an active proton such as an anionic group, the active terminal of the living anionic polymer immediately reacts with the group having these active protons and is deactivated. No polymer is available. Since it is difficult to polymerize a monomer having a group having an active proton as it is in living anionic polymerization, the group having an active proton is polymerized in a protected state, and then the protecting group is deprotected to have an active proton. It is preferable to regenerate the group.

For this reason, in the polymer block A ^3, it is preferable to use a monomer containing a (meth) acrylate having a renewable protecting group an anionic group by deprotection. By using the monomer, it is possible to prevent the above-mentioned inhibition of polymerization at the time of polymerization. Further, the anionic group protected by the protecting group can be regenerated into the anionic group by deprotecting after obtaining the block polymer.

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, a group having an ester bond is preferable as a protective group that can be converted into a carboxyl group, and for example, a primary alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an n-butoxycarbonyl group. Secondary alkoxycarbonyl groups such as isopropoxycarbonyl groups and sec-butoxycarbonyl groups; Tertiary alkoxycarbonyl groups such as t-butoxycarbonyl groups; Phenylalkoxycarbonyl groups such as benzyloxycarbonyl groups; ethoxyethylcarbonyl groups and the like Alkoxyalkylcarbonyl group of.

When the anionic group is a carboxyl group, the monomers that can be used include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 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), nonadecil (meth) acrylate, icosanyl (meth) ) Alkyl (meth) acrylates such as acrylates; phenylalkylene (meth) acrylates such as benzyl (meth) acrylates; alkoxyalkyl (meth) acrylates such as ethoxyethyl (meth) acrylates and the like. These (meth) acrylates can be used alone or in combination of two or more. Further, among these (meth) acrylates, t-butyl (meth) acrylate and benzyl (meth) acrylate are preferable because the conversion reaction to a carboxyl group is easy. Further, considering the availability in the industry, 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. Further, n represents an integer of 1 to 5.

In the living anion polymerization method, when an attempt is made to directly polymerize a (meth) acrylate monomer to the active terminal of a styrene-based polymer having strong nucleophilicity, it may not be possible to polymerize due to a nucleophilic attack on the carbonyl carbon. Therefore, ^{when the (meth) acrylate monomer is polymerized in 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 a batch method as used in the conventional free radical polymerization by adjusting the reaction conditions, and a method of continuous polymerization by a microreactor can also be mentioned. In the microreactor, since the mixture of the polymerization initiator and the monomer is good, the reaction starts at the same time, the temperature is uniform, and the polymerization rate can be made uniform, so that the molecular weight distribution of the produced polymer can be narrowed. At the same time, since the growth end is stable, it becomes easy to produce a block copolymer in which both components of the block are not mixed. 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.
A T-shaped micromixer M1 (FIG. 7) provided with a flow path capable of mixing a plurality of liquids from tube reactors P1 and P2 (7 and 8 in FIG. 1) for the first monomer and the polymerization initiator for initiating polymerization, respectively. Introduced into 1) of 1), the first monomer is subjected to living anionic polymerization in the T-shaped micromixer M1 to form the first polymer (step 1).

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

Next, the first polymer whose reaction was adjusted in the T-shaped micromixer M2 was moved to the T-shaped micromixer M3 (3 in FIG. 1), and in the mixer M3, from the tube reactor P4. The introduced second monomer and the first polymer whose reaction has been adjusted are continuously subjected to living anionic polymerization (step 3).

Then, the reaction is quenched with a compound having an active proton such as methanol to produce a block copolymer.

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 monomer 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 Combined) is obtained.
Next, after adjusting the reactivity of the growth terminal using a reaction modifier, a monomer containing a (meth) acrylate having a renewable protecting group on the anionic group is reacted as the second monomer to cause 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.

A method for regenerating the ester bond of a regenerative protecting group into an anionic group into an anionic group by a deprotection reaction such as hydrolysis will be described in detail.

The hydrolysis reaction of the ester bond proceeds under both acidic and basic conditions, but the conditions are slightly different 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 can be obtained by hydrolysis under basic conditions. be able to. At this time, examples of the basic compound under basic conditions include metal hydroxides such as sodium hydroxide and potassium hydroxide.

When the group having an ester bond is a tertiary alkoxycarbonyl group such as a 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; breathed acids such as trifluoroacetic acid; and Lewis acids such as trimethylsilyltriflate. The reaction conditions for hydrolysis under acidic conditions of the t-butoxycarbonyl group are disclosed, for example, in "The Chemical Society of Japan, 5th Edition, Experimental Chemistry Course 16 Synthesis of Organic Compounds IV".

Further, as a method for converting the t-butoxycarbonyl group into a carboxyl group, a method using a cation exchange resin instead of the above acid can also be mentioned. Examples of the cation exchange resin, e.g., a carboxyl group (-COOH) in the side chain of the polymer chain, resins having a sulfo group (-SO 3 _H) acid groups and the like. Among these, a strongly acidic cation exchange resin having a sulfo group in the side chain of the resin is preferable because the reaction can proceed quickly. Examples of commercially available products of the cation exchange resin that can be used in the present invention include the strongly acidic cation exchange resin "Amberlite" manufactured by Organo Corporation. Since the amount of this cation exchange resin used can be effectively hydrolyzed, it is preferably in the range of 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the polymer represented by the general formula (3), and is 10 parts by mass. A range of ~ 100 parts by mass is more preferable.

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, the phenylalkoxycarbonyl group can be quantitatively regenerated into a carboxyl group by reacting with hydrogen gas as a reducing agent in the presence of a palladium catalyst such as palladium acetate at room temperature.

As described above, since the reaction conditions during the conversion of the type of group to the carboxyl group are different with, for example, t- butyl as a raw material of A ³ (meth) acrylate and n- butyl (meth) acrylate with an ester bond The polymer obtained by copolymerization will have 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 is not hydrolyzed, so that only the t-butoxycarbonyl group can be selectively hydrolyzed to be deprotected to the carboxyl group. It 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.

Further, 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, but the polymer block is used. A block copolymer that is regularly bonded in a group of a certain length 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 for producing 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 ) to 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 :. When it is 450, for example, it is possible to maintain the good ejection stability required when ejecting ink by an inkjet method, and to obtain an ink capable of producing a printed matter having further excellent color development and the like. 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 is in the range of 6 to 30. Is still preferable, and the range of 7 to 25 is most preferable. The number of anionic groups constituting the polymer block ^{(A 3)} is preferably in the range of 3 to 20, still 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 as a molar ratio of the number of moles of anionic groups, 100: 7.5 to 100: 400 is preferable.

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 40 mgKOH / g to 190 mgKOH / g. This is, for example, in obtaining an ink that can maintain the good ejection stability required when ejecting ink by an inkjet method and can produce an even more excellent printed matter in terms of scratch resistance and the like. More preferred.

The acid value of the polymer in the present invention was determined by the same acid value measuring 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 compound can be used, for example, 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 does not need to be 100% neutralized with respect to the acid value of the polymer. Specifically, it is preferable that the polymer (G) is neutralized so that the neutralization rate is 20% to 200%, and 80% to 150% is still preferable.

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

Specifically, as the water, pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, distilled 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 ejected by an inkjet method. It is particularly preferable to obtain an ink capable of producing a clear printed matter having the high ejection stability required for the above.

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, Glycos such as polyethylene glycol and polypropylene glycol; diols such as butanediol, pentanediol, hexanediol and similar diols; glycol esters such as propylene glycol laurate; diethylene glycol monoethyl, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether , Propropylene glycol ethers, dipropylene glycol ethers, and glycol ethers such as cellosolve containing triethylene glycol ethers; butyls such as methanol, ethanol, isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol and 2-butanol. Alcohols such as alcohols, pentyl alcohols, and alcohols of the same family thereof; sulfolanes; lactones such as γ-butyrolactone; lactams such as N- (2-hydroxyethyl) pyrrolidone, etc. are used alone or in combination of two or more. be able to.

Further, as the organic solvent (F), in addition to the above-mentioned one, a water-soluble organic solvent (f1) having a boiling point of 100 ° C. or higher and 200 ° C. or lower and a vapor pressure of 0.5 hPa or higher at 20 ° C. Is preferable in order to obtain a quick-drying effect in which the discharged droplets land on the surface of the cloth and then quickly dry on 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 Examples thereof include ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, 4-methoxy-4-methyl-2-pentanone, ethyl lactate, etc., and two or more of these may be used in combination. Can be done.

Among them, the water-soluble organic solvent (f1) is used for maintaining good dispersion stability of ink and for suppressing deterioration of an ink ejection nozzle provided in an inkjet device, for example, due to the influence of the solvent contained in the ink. , It is preferable to use a water-soluble organic solvent such that the hydrogen bond term δH of HSP (Hansen solubility parameter) is in the range of 6 to 20.

Specific examples of the water-soluble organic solvent having the hydrogen bond term of HSP in 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 more preferably 3. -Methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol.

Examples of the organic solvent that can be used in combination with the aqueous medium (C) include propylene glycol (f2) and glycerin in addition to the water-soluble organic solvent (f1) or together with the water-soluble organic solvent (f1). The combined use of one or more organic solvents (f3) selected from the group consisting of glycerin derivatives, diglycerin and diglycerin derivatives can be used in combination with the quick-drying effect of ink on the cloth and the drying of ink at the ink ejection port. It is preferable to achieve both the effect of preventing coagulation.

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

Among them, using glycerin and polyoxypropylene (n) polyglyceryl ether having n = 8 to 15 as the organic solvent (f3) is excellent in settability of printed matter, and the ink is dried or solidified at the ink ejection port. It is particularly preferable to have the effect of preventing the above.

In the general formula (1) and the general formula (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 it is preferable to use it in the range of 5% by mass to 25% by mass for the settability of the printed matter. It is excellent and is particularly preferable in that it has an effect of preventing the ink from drying and solidifying at the ink ejection port.

The mass ratio of the water-soluble organic solvent (f1), propylene glycol (f2), and the organic solvent (f3) [water-soluble solvent (f1) / propylene glycol (f2)] is 1/25 to 1/1. It is preferable to use it in the range of 1/20 to 1/1, and it is particularly preferable to use it in the range of 1/2 to 1/1 in order to have excellent settability of printed matter and to exert an effect of preventing the ink from drying and solidifying at the ink ejection port. ..

Further, 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 in order to have excellent settability of printed matter and to exert an effect of preventing the ink from drying and solidifying at the ink ejection port. preferable.

In addition to the above-mentioned components, the ink of the present invention can be used as a surfactant (E), a saccharide, a preservative, a viscosity regulator, a pH regulator, a chelating agent, an antioxidant, an ultraviolet absorber, etc. Those containing the additives of can be used.

The surfactant (E) can be used to improve the leveling property of the ink by reducing the surface tension of the ink. Further, the surfactant (E) can prevent the occurrence of streaks in the printed matter by allowing the ink ejected from the ejection port of the inkjet head to satisfactorily wet and spread on the surface after landing on the fabric.

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. It is preferable to use a surfactant.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkylphenyl sulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, sulfate ester salts of higher fatty acid esters, sulfonates of higher fatty acid esters, and higher alcohols. Examples thereof include sulfate ester salts and sulfonates of ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates and the like. Specific examples of these include dodecylbenzene sulfonate, isopropylnaphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol disulfonate and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, and glycerin fatty acid. Oxyethylene adducts of esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkylalkanolamides, acetylene glycols, acetylene glycols. , Polyethylene Glycol Polyethylene Glycol Block Copolymer, etc. Among these are polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene. Preferables are fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid alkylolamides, acetylene glycols, oxyethylene adducts of acetylene glycol, and polyethylene glycol polypropylene glycol block copolymers. Of these, acetylene glycol and an oxyethylene adduct of acetylene glycol are more preferable because they reduce the contact angle of the ink droplets with the recording medium and obtain a good printed matter.

Other surfactants include silicone-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylic acid salts, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Agents; biosurfactants such as spicrysporic acid, ramnolipide, lysolecithin and the like 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 a state in which the surfactant (E) is dissolved in an ink containing water as a main solvent. It is preferable to do so.

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

Examples of the saccharides include monosaccharides and polysaccharides, in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitos, maltose, cellobiose, sucrose, trehalose, maltotriose and the like. Aldonic acid and salts thereof, cyclodextrins and celluloses can be used.

Examples of the preservative include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazolin-3-one (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 collagen, 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, diethylenetriaminetetraacetic 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).

Examples of the antioxidant or ultraviolet absorber include alohanates such as alohanate and methylalohanate, biurets such as biuret, dimethyl biuret and tetramethyl biuret, L-ascorbic acid and salts thereof, and Tinuvin 328 manufactured by Ciba Geigy Co., Ltd. Examples thereof include 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, etc., or oxides of lanthanide.

(Ink manufacturing method)
When the coloring material (B) is a pigment, the ink of the present invention produces an aqueous pigment dispersion containing the pigment at a high concentration, and the aqueous medium (C), the binder resin (A), and the surface activity. 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 for preparing an aqueous pigment dispersion by adding a pigment to a mixture containing a dispersed resin and water and then dispersing the pigment in the mixture using a stirring and dispersing device.
(2) Pigment and dispersion resin are kneaded using a kneader such as a two-roll or mixer, and the obtained kneaded product is added with water and, if necessary, an organic solvent to be mixed with water, and stirred and dispersed. A method for preparing an aqueous pigment dispersion using.
(3) After adding the pigment to the solution obtained by dissolving the dispersion resin in an organic solvent compatible with water such as methyl ethyl ketone and tetrahydrofuran, the pigment is dispersed in the organic solution using a stirring and dispersing device. Then, after phase inversion emulsification using an aqueous medium, the organic solvent is distilled off to prepare an aqueous pigment dispersion.

The kneading machine is not particularly limited, and examples thereof include a Henschel mixer, a pressurized kneader, a Banbury mixer, an intensive mixer, a planetary mixer, and a butterfly mixer.

As the stirring / 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. ..

As the aqueous pigment dispersion, it is possible to form a printed matter having a high image density and excellent dispersion stability by using one containing 5% by mass to 60% by mass of the pigment with respect to the total amount of the aqueous pigment dispersion. It is preferable to use an aqueous pigment dispersion having a content of 10% by mass to 50% by mass, which is preferable for obtaining the ink.

In addition, since the coarse particles contained in the aqueous pigment dispersion cause deterioration of image characteristics, use an aqueous pigment dispersion in which the coarse particles are removed by centrifugation or filtration before and after manufacturing the ink. Is preferable.

When producing the aqueous pigment dispersion, the dispersion step may be followed by an ion exchange treatment or an impurity removal step by an extraneous treatment, followed by a post-treatment. Ionic substances such as cations and anions (divalent metal ions, etc.) can be removed by ion exchange treatment, and impurity-dissolving substances (residual substances during pigment synthesis, excess components in the dispersion liquid composition) can be removed by extraneous treatment. , Resin not adsorbed on organic pigments, foreign substances mixed in, etc.) can be removed. A known ion exchange resin is used for the ion exchange treatment. The ultrafiltration treatment uses a known ultrafiltration membrane and may be either a normal type or a double capacity up type.

The ink of the present invention preferably has a pigment concentration of 1% by mass to 20% by mass in order to obtain a sufficient image density and to ensure good dispersion stability of the pigment in the ink.

The pH of the ink is preferable in order to improve the storage stability and ejection stability of the ink, and to improve the wet spread, print density, and water fastness when printed on a fabric having easy or poor absorption of ink. 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, ink ejection port, ink flow path, etc.) constituting the ink application or ejection device, and reduces the influence when the ink adheres to the skin. On top of that, it is preferably 11.0 or less, more preferably 10.0 or less, and even more preferably 9.5 or less.

The ink is ejected exclusively to the surface of the fabric by an inkjet recording method. Further, since the ink is used for printing on a cloth, it can be suitably used as a so-called printing agent.
In general, the cloth means a woven fabric made by alternately weaving threads made of fibers such as cotton in the vertical direction and the horizontal direction. The ink of the present invention is suitable not only for fabrics in a general sense but also for media composed of fibers such as non-woven fabrics and knitted fabrics. As the material, a cloth made of any natural fiber or synthetic fiber such as cotton, silk, wool, linen, nylon, polyester, polyurethane, rayon, or a cloth in which these are blended can be used.

The printed matter obtained by the method for producing a printed matter of the present invention has excellent added quality and excellent water resistance and fastness, and is therefore used for textile products for home textiles such as clothes, curtains, covers and sheets. be able to.

Hereinafter, the present invention will be described in more detail by way of examples.

<Synthesis example of dispersed resin (P-1)>
A polymer was obtained by introducing a hexane solution of BuLi and a styrene solution in which styrene was previously dissolved in tetrahydrofuran from tube reactors P1 and P2 shown in FIG. 1 into a T-shaped micromixer M1 and performing living anionic polymerization.

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 from the tube reactor P3 as a reaction modifier (α-). Trapped with methylstyrene (α-MeSt)).

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

When producing the block copolymer (PA-1) composition, the reaction temperature was set to 24 ° C. by burying 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 obtained block copolymer (PA-1) composition was hydrolyzed by treating with a cation exchange resin, then distilled off under reduced pressure, and the obtained solid was pulverized to obtain a weight average molecular weight of 2710. , A powdery dispersed resin (P-1) having an acid value of 145 was obtained.

The physical characteristic values of the obtained dispersed resin (P-1) were measured as follows.

(Measuring method of weight average molecular weight (Mw))
It was measured 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 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel 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 amount: 100 μL (THF solution with sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

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

(Measuring method of acid value)
The measurement was performed according to the JIS test method K 0070-1992. It was determined by dissolving 0.5 g of a 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) 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) as pigments. 150 parts by mass of triethylene glycol and 11.5 parts by mass of a 34 mass% potassium hydroxide aqueous solution were charged into a 1.0 L intensive mixer (Nippon Eirich Co., Ltd.), and the rotor peripheral speed was 2.94 m / s. The mixture was kneaded at a peripheral speed of 1 m / s for 60 minutes.

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

<Example 1> Preparation of water-based ink and printed matter 30 parts by mass of the water-based pigment dispersion (A1), 7 parts by mass of a urethane resin composition (nonvolatile content 23% by mass) described later as a binder resin, and Surfinol 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, ACTICIDE B-20 (So Japan) as an antiseptic A water-based ink was obtained by mixing 0.2 parts by mass of (manufactured by Co., Ltd.) and 34.8 parts by mass of ion-exchanged water. The viscosity of the water-based ink at 25 ° C. was 10 mPa · s, and the surface tension was 34 mN / m.

The water-based ink obtained in the examples is filled in the inkjet head of the piezo type inkjet printer, and the vertical line assumed for the surface (x) intersects the cloth from the surface (x) having the ink ejection port of the inkjet head. The distance (gap) to the position (y) was set to 3 mm. As the cloth, cotton broadcloth (manufactured by Color Dyeing Co., Ltd.) was used.

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

<Manufacturing method of binder resin>
Polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 500 parts by mass, 2 , 2-Dimethylol propionic acid 37.7 parts by mass and methyl ethyl ketone 420 parts by mass were added and mixed uniformly. Then, after adding 92.4 parts by mass of tolylene diisocyanate, 0.1 part by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours to obtain a polyurethane (PUD-1) (acid) having a weight average molecular weight of 40,000. An organic solvent solution having a value of 35 mgKOH / g) was obtained. Then, 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 non-volatile content of 23% by mass in which the urethane resin (PUD-1) was dispersed in an aqueous medium was obtained.

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

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

(Measuring method of acid value)
It was determined according to the JIS test method K0070-1992 and under the above-mentioned conditions.

(Measurement method of glass transition temperature)
The glass transition temperature of the urethane resin (PUD-1) was measured using a 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 conical plate type (cone plate type) 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
The static surface tension of the ink was measured under the following conditions using an automatic tensiometer to which the Wilhelmi method was applied.
Measuring device: Automatic tensiometer (CBVP-Z type manufactured by Kyowa Interface Science Co., Ltd.)
Measurement temperature: 25 ° C
Meter: Platinum plate

<Examples 2 to 4> Preparation of water-based 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 values shown in Table 1.

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

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

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

[Evaluation of washing resistance]
The printed matter obtained by the above method is tested according to the A-2 method of JIS L 0844: 2005, and then according to the judgment criteria of the visual inspection method using the gray scale for discoloration and fading of JIS L 0801: 2004. The grade was judged by the 1st to 5th grades. As for the grade, it was evaluated that the first grade had the largest fading and the closer to the fifth grade, the less the fading.

[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 in accordance with JIS L 0849: 2004, and then discoloration and fading of JIS L 0801: 2004. The grades were judged in grades 1 to 5 according to the criteria of the visual perception method using the gray scale for printing. As for the grade, the first grade has the largest fading, and the closer to the fifth grade, the less the fading.

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)

A printed matter is printed on a cloth by an inkjet recording method by printing a water-based ink (excluding active photocurable ink) having a viscosity of 4 mPa · s to 20 mPa · s and a surface tension in the range of 20 mN / m to 40 mN / m. In the printing step, the shortest distance between the ink ejection port of the inkjet head and the fabric is 2 mm or more and 10 mm or less, and the size of one water-based ink droplet ejected from the inkjet head is 10 to 10. range der of 50pl is, the water-based ink styrene is a pigment dispersing agent - those containing acrylic resin, a urethane resin as a binder resin (a), the aqueous medium (C) and a coloring material (B) A method for producing a printed matter, which is characterized by being present. The method for producing a printed matter according to claim 1, wherein the water-based ink contains 1 to 15% by mass of the binder resin (A) with respect to the total amount of the water-based ink. The method for producing a printed matter according to claim 1 or 2, wherein the pigment dispersant is a block polymer represented by the following general formula (3).

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

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