WO2024262321A1 - インクジェット用捺染インク及びインクジェット記録方法 - Google Patents

インクジェット用捺染インク及びインクジェット記録方法 Download PDF

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Publication number
WO2024262321A1
WO2024262321A1 PCT/JP2024/020622 JP2024020622W WO2024262321A1 WO 2024262321 A1 WO2024262321 A1 WO 2024262321A1 JP 2024020622 W JP2024020622 W JP 2024020622W WO 2024262321 A1 WO2024262321 A1 WO 2024262321A1
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Prior art keywords
ink
pigment
group
acid
meth
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PCT/JP2024/020622
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English (en)
French (fr)
Japanese (ja)
Inventor
麻衣子 北出
純平 近藤
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to CN202480028424.0A priority Critical patent/CN121013893A/zh
Priority to JP2024573338A priority patent/JP7722609B2/ja
Publication of WO2024262321A1 publication Critical patent/WO2024262321A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • B41J2/21—Ink jet for multi-colour printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/003—Transfer printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing

Definitions

  • the present invention relates to inkjet textile printing ink and inkjet recording methods.
  • the color development of the white ink i.e., the whiteness
  • the color development of the color inks is also reduced.
  • the coating properties of the white ink such as strength and elongation, are poor, the printed material obtained by printing color inks on the white ink will also crack, resulting in poor quality.
  • inkjet printing devices equipped with ink-circulating inkjet heads have become known as inkjet printing devices in order to prevent clogging of ejection nozzles caused by settling of pigments, resin particles, and the like within the inkjet head.
  • ink-circulating inkjet heads is also increasing for color inks, but in the case of white ink in particular, titanium oxide is often used as the main pigment, and it is necessary to circulate the ink in the passage to prevent sedimentation. Therefore, suitability for the ink-circulating inkjet head is particularly important for white ink.
  • DTF printing Inkjet printing, which prints directly onto fabric.
  • DTF direct-to-film
  • Patent Document 1 discloses a technique in which a transfer film is produced using a specific ink, then the ink is thermally transferred onto a pretreated fabric, and then post-treated to improve fixability.
  • the technology described in Patent Document 1 does not take any measures regarding the strength of the ink coating after printing or its suitability for recycling, and there are cases where defects such as cracks occur when the printed fabric is stretched, or the path becomes clogged due to circulation.
  • the problem that the present invention aims to solve is to provide an inkjet printing ink that does not cause cracks or breaks in the image when the printed material is stretched, and does not clog the path even when the ink is circulated by a circulation type inkjet head.
  • the present invention solves the above-mentioned problems by providing an inkjet textile printing ink comprising a pigment and a binder resin, wherein the binder resin comprises a polyether-based urethane resin, and the ink is applied to a polyethylene terephthalate plate and dried to produce a coating film having a thickness of 15 ⁇ m, and the difference between the indentation depth at 100° C. and the indentation depth at 30° C. is less than 250 nm.
  • An example of the configuration of the present invention that solves the above problem is as follows.
  • Item 1 An inkjet printing ink containing a pigment and a binder resin,
  • the binder resin includes a polyether-based urethane resin,
  • the ink-jet textile printing ink wherein the ink is applied to a polyethylene terephthalate plate and dried to form a coating film having a thickness of 15 ⁇ m, and the difference between the indentation depth at 100° C. and the indentation depth at 30° C. is less than 250 nm.
  • Item 2 The inkjet printing ink according to item 1, wherein the pigment is a white pigment.
  • Item 3 The inkjet printing ink according to item 2, wherein the white pigment is alumina-treated titanium oxide.
  • Item 4 A process of printing the inkjet textile printing ink according to any one of items 1 to 3 onto a film substrate to obtain a transfer film; A method for producing a printed matter, comprising a step of overlapping a receiving surface of a fabric with a printing surface of the transfer film and performing thermal transfer.
  • Item 5 The method for producing a printed matter according to item 4, further comprising the step of applying an adhesive resin to the printing surface of the transfer film.
  • Item 6 A textile print in which an inkjet printing ink containing a pigment and a binder resin is printed on a fabric,
  • the binder resin is a polyether-based urethane resin,
  • the ink is an ink having a thickness of 15 ⁇ m when applied to a polyethylene terephthalate plate and dried, and the difference in indentation depth between the ink at 100° C. and the ink at 30° C. is less than 250 nm.
  • the present invention makes it possible to provide an inkjet printing ink that produces high color density prints, does not crack or break the image when stretched, and does not clog the ink passage when circulating.
  • the present invention also makes it possible to provide a white ink for inkjet textile printing that produces printed matter with high whiteness, does not cause cracks or breaks in the image when stretched, and does not clog the ink path when circulating.
  • FIG. 1 is a schematic diagram of a microreactor used in the present invention.
  • the inkjet printing ink of the present invention is an inkjet printing ink containing a pigment and a binder resin, the binder resin containing a polyether-based urethane resin, and the ink is applied to a polyethylene terephthalate plate and dried to produce a coating film having a thickness of 15 ⁇ m, and the difference between the indentation depth at 100°C and the indentation depth at 30°C is less than 250 nm.
  • Binder resin used in the ink-jet textile printing ink of the present invention is a polyether-based urethane resin.
  • the polyether-based urethane resin is a polyurethane resin using a polyether diol as a polymer polyol component (soft segment).
  • the content of the polyether diol contained in the diol used as a raw material for the polyether-based urethane resin is preferably in the range of 10% by mass to 90% by mass.
  • the polyether-based urethane resin may contain polycarbonate diol, polyester diol, etc. as a raw material as necessary, and from the viewpoint of balance of performance, it is preferable to contain only polyether diol.
  • polyether-based urethane resin it is preferable to use a polyurethane having a hydrophilic group in order to improve the aqueous dispersion stability in the inkjet textile printing ink of the present invention.
  • hydrophilic group those generally called anionic groups, cationic groups, or nonionic groups can be used. Among them, it is preferable to use an anionic group or a cationic group as the hydrophilic group.
  • the anionic group may be, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, or a sulfonate group.
  • a carboxylate group or a sulfonate group that has been partially or completely neutralized with a basic compound or the like in order to maintain good aqueous dispersion stability.
  • Basic compounds that can be used to neutralize the carboxyl and sulfonic acid groups as the anionic groups include, for example, organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, and metal base compounds containing Na, K, Li, Ca, and the like.
  • the organic amines are preferably used as the basic compounds to prevent problems with the washing fastness of the printed image caused by the basic compounds remaining in the printed image (i.e., the dried film) formed by the inkjet textile printing ink of the present invention, and it is more preferable to use organic amines with a boiling point of 100°C or less, such as ammonia and triethylamine.
  • the cationic group may be, for example, a tertiary amino group.
  • acidic compounds that can be used to neutralize some or all of the tertiary amino groups include formic acid and acetic acid.
  • quaternizing agents that can be used to quaternize some or all of the tertiary amino groups include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate.
  • the nonionic group may be, for example, a polyoxyalkylene group such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly(oxyethylene-oxypropylene) group, or a polyoxyethylene-polyoxypropylene group.
  • a polyoxyalkylene group having an oxyethylene unit as the nonionic group in order to further improve hydrophilicity.
  • the polyether-based urethane resin preferably contains 0.5% to 30% by mass of the hydrophilic group relative to the total amount of the polyether-based urethane resin, and it is more preferable to use one containing 1% to 20% by mass in order to obtain an ink with even better aqueous dispersion stability.
  • polyether-based urethane resin a reaction product of a polyol, including a polyether polyol and a polyol having a hydrophilic group, and a polyisocyanate can be used.
  • polyether polyol examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconite sugar, femimellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, hydroxyphthalic acid, and 1,2,3-propanetrithiol.
  • cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclophenylene, or the cyclic ether compounds are polymerized by ring-opening polymerization using a cationic catalyst, a protonic acid, a Lewis acid, or the like as a catalyst.
  • polyether polyol it is preferable to use a polyether polyol such as polytetramethylene ether glycol having a number average molecular weight of 500 to 4000, it is more preferable to use a polyether polyol such as polytetramethylene ether glycol having a number average molecular weight of 1000 to 4000, and it is even more preferable to use polytetramethylene ether glycol having a number average molecular weight of 2000 to 4000.
  • a polyether polyol such as polytetramethylene ether glycol having a number average molecular weight of 500 to 4000
  • polyether polyol such as polytetramethylene ether glycol having a number average molecular weight of 1000 to 4000
  • polytetramethylene ether glycol having a number average molecular weight of 2000 to 4000 it is preferable to use a polyether polyol such as polytetramethylene ether glycol having a number average molecular weight of 2000 to 4000.
  • polyol having a hydrophilic group for example, a polyol having a cationic group, such as a polyol having a tertiary amino group, can be used.
  • a polyol having a cationic group such as a polyol having a tertiary amino group
  • Specific examples of the polyol having a tertiary amino group include N-methyl-diethanolamine and a polyol obtained by reacting a compound having two epoxy groups with a secondary amine.
  • polyol having a hydrophilic group one having an anionic group can be used, such as 1,2-bis(hydroxymethyl)propionic acid or 1,2-bis(hydroxymethyl)butanoic acid.
  • polyol having a hydrophilic group one having a nonionic group can be used, for example, polyethylene glycol or polypropylene glycol having a structural unit derived from ethylene oxide.
  • polystyrene resin In addition to the above-mentioned polyols, other polyols can be used as needed to produce the polyether-based urethane resin.
  • the polyisocyanate that reacts with the polyols including the polyether polyols can be, for example, aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, or aliphatic or alicyclic structure-containing diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate, either used alone or in combination of two or more of them.
  • aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diiso
  • the inkjet textile printing ink of the present invention when used for printing on fabrics such as clothing, it is preferable to use an aliphatic or aliphatic cyclic structure-containing diisocyanate such as isophorone diisocyanate or dicyclohexylmethane diisocyanate as the polyisocyanate in order to further improve the texture of the printed matter, and it is particularly preferable to use dicyclohexylmethane diisocyanate, as this suppresses cracking during coating film stretching and also acts favorably on circulation filterability.
  • diisocyanate such as isophorone diisocyanate or dicyclohexylmethane diisocyanate
  • examples of the chain extender include diamines such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, and N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, Polyamine-based chain extenders such as triethylenetetramine; hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazin
  • glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, neopentyl glycol, sucrose, methylene glycol, glycerin, and sorbitol; phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; and water can also be used.
  • phenols such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone
  • water can also be used.
  • the chain extender can be used during or after the reaction of the polyol with the polyisocyanate.
  • the polyether-based urethane resin is preferably used in the range of 1% to 22% by mass relative to the total amount of the inkjet textile printing ink of the present invention, and more preferably in the range of 8% to 15% by mass in order to prevent clogging over time of the filter installed midway through the ink circulation path.
  • the above polyether-based urethane resin preferably has a viscosity of 300 mPa ⁇ s or less as an aqueous dispersion with a non-volatile content of 20%, more preferably 200 mPa ⁇ s or less, and even more preferably 100 mPa ⁇ s or less. If the viscosity is within this range, it becomes easier to adjust the viscosity of the ink, and the freedom of ink formulation is improved.
  • the polyether-based urethane resin preferably has a glass transition temperature (Tg) of 0° C. or lower, more preferably ⁇ 20° C. or lower, even more preferably ⁇ 40° C. or lower, and particularly preferably ⁇ 50° C. or lower.
  • Tg glass transition temperature
  • the temperature is preferably from -95 to -60°C, and more preferably from -90 to -70°C.
  • the glass transition temperature can be measured in accordance with JIS K 7121 using a differential scanning calorimeter (DSC).
  • the polyether-based urethane resin preferably has a flow initiation temperature of 150° C. or higher, more preferably 160° C. or higher, even more preferably 170° C. or higher, and particularly preferably 180° C. or higher.
  • a flow initiation temperature is within this range, the resin is less likely to flow when heated on a fabric, and therefore cracks in the coating film are less likely to occur.
  • An example of a method for adjusting the flow initiation temperature to a high level is to use a polyisocyanate having high crystallinity, such as dicyclohexylmethane diisocyanate. More specifically, the temperature is preferably 170 to 195°C, and more preferably 175 to 190°C.
  • the flow starting temperature can be measured for a dried resin using a flow tester "CFT-500A” manufactured by Shimadzu Corporation (using a die with a diameter of 1 mm and a length of 1 mm, a load of 98 N, and a temperature rise rate of 3°C/min).
  • the polyether urethane resin preferably has an acid value of 5 to 40 mgKOH/g, more preferably 8 to 30 mgKOH/g, even more preferably 10 to 24 mgKOH/g, and particularly preferably 10 to 20 mgKOH/g.
  • the acid value is within this range, the ink dispersion stability is good, and clogging over time of the filter installed in the ink circulation path is easily suppressed.
  • the polyether-based urethane resin preferably has a weight-average molecular weight in the range of 10,000 to 400,000, and it is more preferable to use one in the range of 40,000 to 300,000 in order to prevent clogging over time of the filter installed in the ink circulation path.
  • the polyether-based urethane resin is dispersed as particles in an aqueous medium, and the particle diameter is preferably 70 ⁇ m or more, and more preferably 75 ⁇ m or more, but is not limited to this.
  • the particle diameter of the polyether-based urethane resin is the cumulative frequency 50% diameter (D50) value measured by dynamic light scattering.
  • the inkjet textile printing ink of the present invention can also contain a crosslinking agent, which will be described later, for the purpose of further improving abrasion resistance, such as washing fastness.
  • a crosslinking agent it is preferable to use a polyether-based urethane resin having a functional group capable of undergoing a crosslinking reaction with the functional group of the crosslinking agent.
  • ink containing a crosslinking agent may crosslink within the circulation path of the ink circulation type inkjet head, it is preferable to use ink that does not contain the crosslinking agent in order to prevent clogging of the filter installed within the circulation path.
  • the inkjet textile printing ink of the present invention may contain a binder resin other than the polyether-based urethane resin, as long as the effect of the present invention is not impaired.
  • the other binder resins include polyurethane resins such as polycarbonate-based urethane resins and polyester-based urethane resins, acrylic resins, and olefin resins.
  • a reaction product of a polyol including a polycarbonate polyol and a polyisocyanate can be used.
  • a reaction product of a polyol including a polycarbonate polyol and a polyol having a hydrophilic group and a polyisocyanate can be used.
  • a reaction product of a polyol including a polycarbonate polyol and a polyisocyanate and a chain extender such as a polyamine can be used.
  • the polycarbonate polyol can be, for example, a reaction product of a carbonate ester and a low molecular weight polyol, preferably a linear aliphatic diol.
  • the carbonate ester that can be used includes methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, etc.
  • Relatively low molecular weight dihydroxy compounds such as bisphenol A, bisphenol F, and 4,4'-biphenol, as well as polyether polyols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol, and polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.
  • polyether polyols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol
  • polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, and polycaprolactone
  • the polyisocyanate that can be used is the same as the polyisocyanate having a hydrophilic group that can be used for the polyether-based urethane resin described above.
  • the same polyol having a hydrophilic group that can be used for the polyether-based urethane resin described above can be used.
  • chain extenders such as polyamines include diamines such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, and N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, and dipropylenetriamine; , triethylenetetramine; hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic
  • the polyamine is preferably used in such a range that the equivalent weight of the amino groups in the polyamine is 0.01 to 1.0 (equivalent ratio) relative to the equivalent weight of the isocyanate groups in the urethane prepolymer, which is the reaction product of the polyol and polyisocyanate, more preferably 0.01 to 0.5 (equivalent ratio), and even more preferably 0.01 to 0.3 (equivalent ratio).
  • polyester-based urethane resin a reaction product of a polyol, including a polyester polyol, and a polyisocyanate can be used.
  • a reaction product of a diol and a dicarboxylic acid a product obtained by dehydration condensation reaction of a hydroxycarboxylic acid alone or in combination with a diol or a dicarboxylic acid, a ring-opening polymerization reaction product of a cyclic ester compound such as ⁇ -caprolactone, etc. can be used.
  • diols examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone, and alkylene oxide adducts thereof.
  • dicarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, and 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid.
  • hydroxycarboxylic acid examples include p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, etc.
  • the other polyols include relatively low molecular weight polyols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and alkylene oxide adducts thereof, glycerin, trimethylolethane, trimethylolpropane, sorbitol, and pentaerythritol, which may be used alone or in combination of two
  • acrylic resin there are no particular limitations on the acrylic resin, and it is possible to use homopolymers or copolymers of (meth)acrylates, copolymers of (meth)acrylates and other vinyl monomers, etc.
  • the inkjet textile printing ink of the present invention contains a pigment.
  • the pigment is not particularly limited, and any known and commonly used pigment such as an organic pigment or an inorganic pigment that is normally used in conventional screen printing or in aqueous inkjet recording inks can be used.
  • a colorant in which the pigment is coated with a resin can also be used.
  • the color ink includes pigments having a color other than white, and includes black ink.
  • the pigment may be either a non-acid-treated pigment or an acid-treated pigment, and may be in either a dry powder or wet cake form.
  • inorganic pigments examples include iron oxide, titanium oxide, and carbon black produced by the contact method, furnace method, or thermal method.
  • organic pigment for example, azo pigments (including azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), lake pigments (for example, basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used.
  • azo pigments including azo lake, insoluble azo pigment, condensed azo pigment, chelate azo pigment, etc.
  • polycyclic pigments for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments
  • pigments used in black inks include Mitsubishi Chemical Corporation's No. 2300, No. 2200B, No. 900, No. 980, No. 960, No. 950, No. 33, No. 40, No. 45, No. 45L, and No. 52, HCF88, MCF88, MA7, MA8, MA100, etc. manufactured by Columbia; Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc.
  • pigments used in yellow ink include C.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, and 185.
  • pigments used in magenta inks include C.I. Pigment Violet 19, C.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 mixtures or solid solutions of at least two or more pigments selected from these pigments.
  • pigments used in cyan ink include C.I. Pigment Blue 1, 2, 3, 15, 15:3, 15:4, 15:6, 16, 22, 60, 63, and 66.
  • pigments used in the red ink include one or more selected from the group consisting of C.I. Pigment Red 17, 49:2, 112, 149, 150, 177, 178, 179, 188, 254, 255, and 264.
  • pigments used in orange ink include C.I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, 71, 73, and 81.
  • pigments used in green ink include C.I. Pigment Green 7, 10, 36, 58, and 59.
  • pigments used in violet inks include C.I. Pigment Violet 19, 23, 32, 33, 36, 38, 43, and 50.
  • the ink of the present invention is preferably a white ink that contains a white pigment as a pigment.
  • white pigments that can be used in the white ink include alkaline earth metal sulfates, carbonates, finely powdered silicic acid, synthetic silicates, and other silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay, and the like. These may be surface-treated. Among these, titanium oxide is preferred, and alumina-treated titanium oxide is more preferred.
  • the pigments mentioned above can be used alone or in combination of two or more kinds.
  • a means be taken to disperse the pigment well in an aqueous medium such as water.
  • the means include, for example: (i) A method in which a pigment is dispersed in an aqueous medium such as water together with a pigment dispersant by a dispersion method described later; (ii) A method in which a self-dispersing pigment in which a dispersibility-imparting group (hydrophilic functional group and/or a salt thereof) is bonded to the surface of the pigment directly or indirectly via an alkyl group, an alkyl ether group, an aryl group, or the like, is dispersed and/or dissolved in an aqueous medium such as water.
  • a self-dispersing pigment in which a dispersibility-imparting group (hydrophilic functional group and/or a salt thereof) is bonded to the surface of the pigment directly or indirectly via an alkyl group, an alkyl ether group, an aryl group, or the like, is dispersed and/or dissolved in an aqueous medium such as water.
  • the self-dispersing pigment may be, for example, a pigment that has been subjected to a physical or chemical treatment to bond (graft) a dispersibility-imparting group or an active species having a dispersibility-imparting group to the surface of the pigment.
  • the self-dispersing pigment may be produced, for example, by vacuum plasma treatment, oxidation treatment with hypohalous acid and/or hypohalite salts, oxidation treatment with ozone, or a wet oxidation method in which the pigment surface is oxidized with an oxidizing agent in water, or a method in which a carboxyl group is bonded via a phenyl group by bonding p-aminobenzoic acid to the pigment surface.
  • Water-based inks containing self-dispersing pigments do not need to contain the pigment dispersant, so there is almost no foaming caused by the pigment dispersant, and it is easy to prepare inks with excellent ejection stability.
  • water-based inks containing self-dispersing pigments are easy to handle and can contain more pigment because the significant increase in viscosity caused by the pigment dispersant is suppressed, so they can be used to produce printed materials with high print density.
  • Microjet CW-1 (trade name; manufactured by Orient Chemical Industries Co., Ltd.), CAB-O-JET 200, and CAB-O-JET 300 (all trade names; manufactured by Cabot Corporation).
  • the pigment is preferably used in an amount ranging from 1% to 20% by mass, and more preferably from 2% to 15% by mass, based on the total amount of the ink, in order to maintain the excellent dispersion stability of the pigment and improve the print density and washability of the printed matter.
  • the pigment dispersant has a function of dispersing the pigment.
  • the pigment dispersant may be, for example, polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- ⁇ -methylstyrene-acrylic acid copolymers, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, or salts of the aqueous resins.
  • acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, sty
  • the pigment dispersant may be, for example, the Ajisper PB series from Ajinomoto Fine-Techno Co., Ltd., the Disperbyk series from BYK Japan, the EFKA series from BASF, the SOLSPERSE series from Lubrizol Japan, and the TEGO series from Evonik.
  • the polymer (E) described below can be used to significantly reduce coarse particles, thereby imparting the good ejection stability required when ejecting the ink using an inkjet method.
  • the polymer (E) one having an anionic group can be used, and in particular, it is preferable to use a polymer with a number average molecular weight in the range of 1000 to 6000 that has a solubility in water of 0.1 g/100 ml or less and is capable of forming fine particles in water when the neutralization rate of the anionic group with a basic compound is 100%.
  • the solubility of the polymer (E) in water was defined as follows. That is, 0.5 g of polymer (E) with particle size adjusted to the range of 250 ⁇ m to 90 ⁇ m using sieves with mesh sizes of 250 ⁇ m and 90 ⁇ m was sealed in a bag made of processed 400 mesh wire mesh, immersed in 50 ml of water, and left to stand for 24 hours with gentle stirring at a temperature of 25°C. After immersion for 24 hours, the 400 mesh wire mesh with polymer (E) sealed inside was dried for 2 hours in a dryer set at 110°C. The change in weight of the 400 mesh wire mesh with polymer (E) sealed inside before and after immersion in water was measured, and the solubility was calculated using the following formula.
  • the acid value of the polymer (E) is measured in advance by an acid value measurement method based on JIS test method K 0070-1992. Specifically, 0.5 g of the polymer (E) is dissolved in tetrahydrofuran, and the acid value is determined by titration with a 0.1 M alcoholic solution of potassium hydroxide using phenolphthalein as an indicator.
  • the particle diameter of the fine particles is preferably in the range of 5 nm to 1000 nm, more preferably in the range of 7 nm to 700 nm, and most preferably in the range of 10 nm to 500 nm. Furthermore, the narrower the particle size distribution of the fine particles, the better the dispersion stability tends to be, but even if the particle size distribution is broad, it is possible to obtain an ink with better dispersion stability than before.
  • the particle diameter and particle size distribution were measured using a dynamic light scattering particle size distribution measuring device (Microtrack Particle Size Distribution Meter UPA-ST150, dynamic light scattering particle size measuring device manufactured by Nikkiso Co., Ltd.), in the same manner as in the measurement method for the fine particles.
  • a dynamic light scattering particle size distribution measuring device Microtrack Particle Size Distribution Meter UPA-ST150, dynamic light scattering particle size measuring device manufactured by Nikkiso Co., Ltd.
  • the neutralization rate of polymer (E) was determined by the following formula:
  • the acid value of the polymer (E) was measured based on JIS test method K 0070-1992. Specifically, 0.5 g of the sample was dissolved in tetrahydrofuran, and the acid value was determined by titrating with 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.
  • the number average molecular weight of the polymer (E) is preferably in the range of 1000 to 6000, more preferably 1300 to 5000, and more preferably 1500 to 4500, which can effectively suppress the aggregation of the pigment in the solvent (C) and is more preferable for obtaining an ink with good dispersion stability of the pigment.
  • the number average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography), specifically, under the following conditions:
  • Measurement was performed by gel permeation chromatography (GPC) under the following conditions.
  • Measurement device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
  • Column The following columns manufactured by Tosoh Corporation were used, connected in series.
  • TKgel G5000 (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D. x 30cm) x 1
  • Detector RI (differential refractometer) Column temperature: 40°C Eluent: tetrahydrofuran Flow rate: 1.0 mL/min Injection volume: 100 ⁇ L (sample concentration 0.4% by mass in tetrahydrofuran solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • the polymer (E) used is preferably one that has a surface tension of 30 dyn/cm or more, more preferably 40 dyn/cm or more, and particularly preferably one that has a surface tension of 65 dyn/cm to 75 dyn/cm, which is close to the surface tension of water.
  • the surface tension is the value measured for a 100% neutralized polymer solution by adding 1 g of polymer (E) to water and then adding a 0.1 mol/L aqueous potassium hydroxide solution sufficient to neutralize the resulting acid value 100%.
  • the polymer (E) may be any polymer that is insoluble or poorly soluble in water when not neutralized and forms fine particles when 100% neutralized, and is not particularly limited as long as it has hydrophobic groups in one molecule in addition to anionic groups, which are hydrophilic groups.
  • polymer (E) is a block polymer having a polymer block having a hydrophobic group and a polymer block having an anionic group.
  • 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, even if the polymer has the same acid value, those with a low molecular weight tend to have high solubility in water, and those with a high molecular weight tend to have low solubility in water. For this reason, in the present invention, polymer (E) is specified by its solubility in water.
  • the polymer (E) may be a homopolymer, but is preferably a copolymer, and may be a random polymer, a block polymer, or an alternating polymer, but is preferably a block polymer.
  • the polymer may also be a branched polymer, but is preferably a linear polymer.
  • the polymer (E) is preferably a vinyl polymer from the viewpoint of design freedom, and the method for producing a vinyl polymer having the molecular weight and solubility characteristics desired in the present invention is preferably by using "living polymerization” such as living radical polymerization, living cationic polymerization, or living anionic polymerization.
  • the polymer (E) is preferably a vinyl polymer produced using a (meth)acrylate monomer as one of the raw materials, and the method for producing such a vinyl polymer is preferably living radical polymerization or living anionic polymerization, and further preferably living anionic polymerization from the viewpoint of being able to more precisely design the molecular weight of the block polymer and each segment.
  • the polymer (E) produced by living anionic polymerization is specifically a polymer represented by general formula (3).
  • A1 represents an organolithium initiator residue
  • A2 represents a polymer block having a hydrophobic group
  • A3 represents a polymer block containing an anionic group
  • n represents an integer of 1 to 5
  • B represents an aromatic group or an alkyl group.
  • A1 represents an organic lithium initiator residue.
  • organic lithium initiators include alkyl lithiums such as methyl lithium, ethyl lithium, propyl lithium, butyl lithium (n-butyl lithium, sec-butyl lithium, iso-butyl lithium, tert-butyl lithium, etc.), pentyl lithium, hexyl lithium, methoxymethyl lithium, and ethoxymethyl lithium; phenyl alkylene lithiums such as benzyl lithium, ⁇ -methylstyryl lithium, 1,1-diphenyl-3-methylpentyl lithium, 1,1-diphenylhexyl lithium, and phenylethyl lithium; alkenyl lithiums such as vinyl lithium, allyl lithium, propenyl lithium, and butenyl lithium; alkynyl lithiums such as ethynyl lithium, butynyl lithium, pentynyl lithium, and hexynyl lithium; aryl lithiums
  • organolithium initiators In organolithium initiators, the bond between the organic group and lithium is cleaved, generating an active end on the organic group side, from which polymerization begins. Therefore, an organic group derived from the organolithium is bonded to the end of the resulting polymer.
  • the organic group derived from the organolithium bonded to the polymer end is referred to as an organolithium initiator residue.
  • the organolithium initiator acid group is a methyl group
  • the organolithium initiator acid group is a butyl group.
  • A2 represents a polymer block having a hydrophobic group.
  • A2 is preferably a group that is highly adsorbable to a pigment when it comes into contact with the pigment, in addition to the purpose of achieving an appropriate balance in solubility, and from that viewpoint, A2 is preferably a polymer block of a monomer having an aromatic ring or a heterocyclic ring.
  • the polymer block of a monomer having an aromatic ring or a heterocyclic ring is specifically a polymer block of a homopolymer or copolymer obtained by homopolymerizing or copolymerizing a monomer having an aromatic ring, such as a styrene-based monomer, or a monomer having a heterocyclic ring, such as a vinylpyridine-based monomer.
  • Examples of monomers with an aromatic ring include styrene-based monomers such as styrene, p-tert-butyl, styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-tert-butoxystyrene, m-tert-butoxystyrene, p-tert-(1-ethoxymethyl)styrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, ⁇ -methylstyrene, and p-methyl- ⁇ -methylstyrene, as well as vinylnaphthalene and vinylanthracene.
  • styrene-based monomers such as styrene, p-tert-butyl, styrene, o-methylstyrene, p-methyls
  • examples of monomers having a heterocycle include vinylpyridine monomers such as 2-vinylpyridine and 4-vinylpyridine. These monomers can be used alone or in combination of two or more.
  • A3 represents a polymer block containing an anionic group.
  • A3 has the purpose of imparting appropriate solubility, as well as the purpose of imparting dispersion stability in water when a pigment dispersion is formed.
  • the anionic group in the polymer block A3 may be, for example, a carboxyl group, a sulfonic acid group, or a phosphoric acid group.
  • a carboxyl group is preferred because of its preparation and the wide variety of monomer varieties and easy availability.
  • Two carboxyl groups may be dehydrated and condensed intramolecularly or intermolecularly to form an acid anhydride group.
  • the method of introducing the anionic group of A3 is not particularly limited.
  • the anionic group when it is a carboxyl group, it may be a polymer block (PB1) of a homopolymer or copolymer obtained by homopolymerizing (meth)acrylic acid or copolymerizing it with other monomers, or it may be a polymer block (PB2) of a homopolymer or copolymer obtained by homopolymerizing or copolymerizing (meth)acrylate having a protecting group that can be regenerated to an anionic group by deprotection, in which some or all of the protecting groups that can be regenerated to an anionic group are regenerated to an anionic group.
  • the (meth)acrylic acid used in the polymer block A3 is a general term for acrylic acid and methacrylic acid
  • (meth)acrylate is a general term for acrylate and methacrylate.
  • (meth)acrylic acid and (meth)acrylates include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, allyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-tridecyl (meth)acrylate, n-methyl (meth)acrylate, n-methyl (meth)acrylate, n-ethylhexyl ...
  • living anionic polymerization if the monomer used has a group with an active proton, such as an anionic group, the active end of the living anionic polymerization polymer immediately reacts with the group with an active proton and is deactivated, so no polymer can be obtained. Since it is difficult to polymerize a monomer with a group with an active proton as is in living anionic polymerization, it is preferable to polymerize the group with the active proton in a protected state, and then regenerate the group with the active proton by deprotecting the protecting group.
  • an active proton such as an anionic group
  • a monomer containing a (meth)acrylate having a protecting group that can be regenerated to an anionic group by deprotection By using such a monomer, the aforementioned inhibition of polymerization can be prevented during polymerization.
  • the anionic group protected by the protecting group can be regenerated to an anionic group by deprotecting it after obtaining the block polymer.
  • the carboxyl group can be regenerated by esterifying the carboxyl group and then deprotecting it by hydrolysis or the like in a subsequent process.
  • the protecting group that can be converted to a carboxyl group is preferably a group having an ester bond, and examples of such groups include primary alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, and n-butoxycarbonyl; secondary alkoxycarbonyl groups such as isopropoxycarbonyl and sec-butoxycarbonyl; tertiary alkoxycarbonyl groups such as t-butoxycarbonyl; phenylalkoxycarbonyl groups such as benzyloxycarbonyl; and alkoxyalkylcarbonyl groups such as ethoxyethylcarbonyl.
  • the monomers that can be used are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate)
  • the acrylate include alkyl (meth)acrylates such as ethyl (meth)acrylate, tridecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecy
  • (meth)acrylates can be used alone or in combination of two or more.
  • t-butyl (meth)acrylate and benzyl (meth)acrylate are preferred because they are easily converted into a carboxyl group.
  • t-butyl (meth)acrylate is more preferred in terms of industrial availability.
  • B represents an aromatic group or an alkyl group having 1 to 10 carbon atoms. Also, n represents an integer from 1 to 5.
  • reaction regulator is used to adjust the nucleophilicity before polymerizing the (meth)acrylate monomer.
  • B in general formula (3) is a group derived from the reaction regulator. Specific examples of reaction regulators include diphenylethylene, ⁇ -methylstyrene, and p-methyl- ⁇ -methylstyrene.
  • Living anionic polymerization can be carried out by adjusting the reaction conditions in a batch manner as used in conventional free radical polymerization, or it can be carried out in a continuous polymerization method using a microreactor.
  • the polymerization initiator and monomer have good mixability, so the reactions start simultaneously, and the temperature is uniform and the polymerization rate can be made uniform, making it possible to narrow the molecular weight distribution of the polymer produced.
  • the growing end is stable, making it easy to produce block copolymers in which the two components of the block do not mix.
  • the reaction temperature is well controllable, making it easy to suppress side reactions.
  • FIG. 1 is a schematic diagram of a microreactor.
  • a first monomer and a polymerization initiator that starts polymerization are introduced from tube reactors P1 and P2 (7 and 8 in FIG. 1), respectively, into a T-shaped micromixer M1 (1 in FIG. 1) equipped with a flow path capable of mixing a plurality of liquids, and the first monomer is subjected to living anionic polymerization in the T-shaped micromixer M1 to form a first polymer (Step 1).
  • the obtained first polymer is transferred to a T-shaped micro mixer M2 (2 in FIG. 1), and in the mixer M2, the growing end of the obtained polymer is trapped by a reaction adjuster introduced from a tube reactor P3 (9 in FIG. 1) to adjust the reaction (step 2).
  • the number n in the general formula (3) can be controlled by the type and amount of the reaction regulator.
  • the first polymer that has been subjected to reaction control in the T-shaped micromixer M2 is transferred to the T-shaped micromixer M3 (3 in FIG. 1), and within the mixer M3, the second monomer introduced from the tube reactor P4 and the first polymer that has been subjected to reaction control are continuously subjected to living anionic polymerization (step 3).
  • reaction is quenched with a compound that has an active proton, such as methanol, to produce a block copolymer.
  • a compound that has an active proton such as methanol
  • a monomer having an aromatic ring or a heterocycle is used as the first monomer, and reacted with an organolithium initiator as the initiator to obtain a polymer block of the monomer having an aromatic ring or a heterocycle A2 (having an organic group, which is a residue of the organolithium initiator A1, bonded to one end of the polymer block A2).
  • a monomer containing a (meth)acrylate having a renewable protecting group on the anionic group is reacted as the second monomer to obtain a polymer block.
  • the anionic groups are regenerated by a deprotection reaction such as hydrolysis, thereby obtaining the A3, i.e., the polymer block containing the anionic groups.
  • ester bonds proceeds under both acidic and basic conditions, but the conditions vary slightly depending on the group that has an ester bond.
  • the group that has 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 carrying out hydrolysis under basic conditions.
  • basic compounds that provide basic conditions include metal hydroxides such as sodium hydroxide and potassium hydroxide.
  • a carboxyl group can be obtained by hydrolysis under acidic conditions.
  • acidic compounds that can be used under acidic conditions include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; Brösted acids such as trifluoroacetic acid; and Lewis acids such as trimethylsilyl triflate. Reaction conditions for hydrolysis of a t-butoxycarbonyl group under acidic conditions are disclosed, for example, in "Experimental Chemistry Lectures 16: Synthesis of Organic Compounds IV," 5th Edition, edited by the Chemical Society of Japan.
  • a method for converting a t-butoxycarbonyl group into a carboxyl group a method using a cation exchange resin instead of the above-mentioned acid can be mentioned.
  • the cation exchange resin include resins having an acid group such as a carboxyl group (-COOH) or a sulfo group (-SO 3 H) on the side chain of the polymer chain.
  • a cation exchange resin exhibiting strong acidity and having a sulfo group on the side chain of the resin is preferred because it can accelerate the progress of the reaction.
  • Examples of commercially available cation exchange resins that can be used in the present invention include the strong acid cation exchange resin "Amberlite" manufactured by Organo Corporation.
  • the amount of this cation exchange resin used is preferably in the range of 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass of the polymer represented by the general formula (3) because it can be effectively hydrolyzed.
  • the group having an ester bond is a phenylalkoxycarbonyl group such as a benzyloxycarbonyl group
  • it can be converted to a carboxyl group by carrying out a hydrogenation reduction reaction.
  • the reaction conditions are room temperature, in the presence of a palladium catalyst such as palladium acetate, and using hydrogen gas as a reducing agent to quantitatively regenerate the phenylalkoxycarbonyl group into a carboxyl group.
  • the reaction conditions for conversion to a carboxyl group differ depending on the type of group having an ester bond.
  • a polymer obtained by copolymerizing t-butyl (meth)acrylate and n-butyl (meth)acrylate as the raw materials for A3 will have t-butoxycarbonyl groups and n-butoxycarbonyl groups.
  • the acid value of the hydrophilic block (A3) can be adjusted by appropriately selecting a monomer containing a (meth)acrylate that has a regenerable protecting group on the anionic group, which is the raw material monomer for A3.
  • the polymer (E) represented by the general formula (3) it is advantageous to use a block copolymer in which the polymer blocks are regularly bonded in a certain length of aggregates, rather than a random copolymer in which the polymer blocks (A2) and (A3) are randomly arranged and bonded, in order to improve the stability of the aqueous pigment dispersion in which the pigment is dispersed in water by the polymer (E).
  • the aqueous pigment dispersion is a raw material used in the production of ink, and may be a liquid in which the pigment is dispersed in water at a high concentration by the polymer (E).
  • the molar ratio A2:A3 of the polymer block (A2) and the polymer block (A3) is preferably in the range of 100:10 to 100:500, and it is more preferable for A2:A3 to be 100:10 to 100:450 in order to obtain an ink that can maintain the good ejection stability required when ejecting ink by an inkjet method, and can produce printed matter with even better color development, etc.
  • the number of aromatic or heterocyclic monomers constituting the polymer block (A2) is preferably in the range of 5 to 40, more preferably in the range of 6 to 30, and most preferably in the range of 7 to 25.
  • the number of anionic groups constituting the polymer block (A3) is preferably in the range of 3 to 20, more preferably in the range of 4 to 17, and most preferably in the range of 5 to 15.
  • the molar ratio A2:A3 of the polymer block (A2) and the polymer block (A3) expressed as the molar ratio of the number of moles of aromatic rings or heterocycles constituting the polymer block (A2) to the number of moles of anionic groups constituting the polymer block (A3), is preferably 100:7.5 to 100:400.
  • the acid value of the polymer (E) represented by the general formula (3) is preferably 40 mgKOH/g to 400 mgKOH/g, more preferably 40 mgKOH/g to 300 mgKOH/g, and more preferably 40 mgKOH/g to 190 mgKOH/g, which is more preferable for obtaining an ink that can maintain the good ejection stability required when ejecting ink by an inkjet method, and can produce printed matter that is even more excellent in terms of abrasion resistance, etc.
  • the acid value of the polymer in the present invention was determined using the same acid value measurement method as the method for measuring the fine particles of polymer (E) described above.
  • the anionic groups of the polymer (E) are neutralized.
  • any known basic compound can be used as the basic compound for neutralizing the anionic groups of the polymer (E), including inorganic basic substances such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, and organic basic compounds such as ammonia, triethylamine, and alkanolamines.
  • inorganic basic substances such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide
  • organic basic compounds such as ammonia, triethylamine, and alkanolamines.
  • the neutralization amount of the polymer (E) present in the aqueous pigment dispersion does not need to be 100% relative to the acid value of the polymer. Specifically, it is preferable that the polymer (E) is neutralized so that the neutralization rate is 20% to 200%, and more preferably 80% to 150%.
  • the polymer (E) can also be used preferably as a dispersion aid in the ink, rather than as a dispersant in the aqueous pigment dispersion.
  • the polymer (E) can be added when the pigment dispersion is manufactured, or when the ink is made.
  • the inkjet textile printing ink of the present invention may contain other ink components in addition to the pigment and binder resin described above.
  • inks containing other additives such as water, water-soluble solvents, surfactants, dispersing aids, sugars, preservatives, viscosity adjusters, pH adjusters, chelating agents, dispersing aids, antioxidants, and ultraviolet absorbers can be used as necessary.
  • water As the water, specifically, pure water or ultrapure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, distilled water, etc. can be used.
  • water-soluble solvent examples include cellosolves containing glycerin, diglycerin, polyglycerin, diglycerin fatty acid esters, polyoxypropylene (n) polyglyceryl ethers, polyoxyethylene (n) polyglyceryl ethers, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, pentanediol, hexane
  • water-soluble solvent among the above, it is preferable to use glycerin, diglycerin, polyglycerin, diglycerin fatty acid ester, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and propylene glycol, and it is preferable to use a combination of glycerin and ethylene glycol or propylene glycol in order to obtain an ink that penetrates into a recording medium such as a fabric and dries easily, and that can be prevented from drying or solidifying in the nozzle or filter of an ink circulation type inkjet head.
  • the water and water-soluble solvent form the aqueous medium of the inkjet textile printing ink of the present invention.
  • the aqueous medium is preferably used in the range of 50% to 95% by mass relative to the total amount of the ink, and is particularly preferably used in the range of 65% to 95% by mass, in order to prevent the ink from drying near the nozzle, to easily adjust the ease of drying after landing on the recording medium, and to obtain an ink that is clear and capable of producing printed matter with a good texture, especially when used for printing on fabric.
  • the aqueous medium also includes the water and water-soluble solvent contained in the pigment dispersion and binder resin.
  • the surfactant can be used to improve the leveling property of the ink by reducing the surface tension of the ink, etc. Furthermore, the surfactant can prevent the occurrence of mottle in the printed matter by allowing the ink discharged from the discharge port of the inkjet head to wet and spread well on the surface of the fabric after it lands on the fabric.
  • surfactant various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used, and it is preferable to use anionic surfactants and nonionic surfactants.
  • anionic surfactant examples include alkylbenzenesulfonates, alkylphenylsulfonates, alkylnaphthalenesulfonates, higher fatty acid salts, sulfates of higher fatty acid esters, sulfonates of higher fatty acid esters, sulfates and sulfonates of higher alcohol ethers, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, and polyoxyethylene alkyl ether phosphates.
  • dodecylbenzenesulfonates include dodecylbenzenesulfonates, isopropylnaphthalenesulfonates, monobutylphenylphenol monosulfonates, monobutylbiphenylsulfonates, and dibutylphenylphenol disulfonates.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylol amides, alkyl alkanol amides, acetylene glycol, oxyethylene adducts of acetylene glycol, polyethylene glycol polypropylene glycol block copolymers, and the like.
  • acetylene glycol and oxyethylene adducts of acetylene glycol are more preferred because they reduce the contact angle of ink droplets with the recording medium and produce good printed matter.
  • surfactants that can be used include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; and biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • silicone surfactants such as polysiloxane oxyethylene adducts
  • fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers
  • biosurfactants such as spiculisporic acid, rhamnolipids, and lysolecithin.
  • a surfactant with an HLB in the range of 4 to 20 In order to stably maintain the state in which the surfactant is dissolved in the ink, which has water as the main solvent, it is preferable to use a surfactant with an HLB in the range of 4 to 20.
  • the surfactant is preferably used in the range of 0.001% to 2% by mass, more preferably 0.001% to 1.5% by mass, and more preferably 0.1% to 1.5% by mass, relative to the total amount of the ink.
  • An inkjet ink containing the surfactant in the above range has good wettability of the ejected droplets on the fabric surface, has sufficient wet-spreading on the fabric, and is preferable in terms of preventing mottle in the printed matter. Furthermore, an ink containing the surfactant in the above range has the effect of improving wettability to the fabric.
  • Sugars include monosaccharides and polysaccharides, such as glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitose, maltose, cellobiose, sucrose, trehalose, maltotriose, and also alginic acid and its salts, cyclodextrins, and celluloses.
  • monosaccharides and polysaccharides such as glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitose, maltose, cellobiose, sucrose, trehalose, maltotriose, and also alginic acid and its salts, cyclodextrins, and celluloses.
  • Preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzisothiazolin-3-one (Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, and Proxel DL, both from Arch Chemicals).
  • viscosity modifiers include mainly water-soluble natural or synthetic polymers such as carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic, and starch.
  • pH adjusters include collidine, imidazole, phosphoric acid, 3-(N-morpholino)propanesulfonic acid, tris(hydroxymethyl)aminomethane, and boric acid.
  • chelating agents include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramildiacetic acid, 1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid, and salts thereof (including hydrates).
  • antioxidants or UV absorbers examples include allophanates such as allophanate and methyl allophanate, biurets such as biuret, dimethyl biuret, and tetramethyl biuret, L-ascorbic acid and its salts, Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, and oxides of lanthanides.
  • allophanates such as allophanate and methyl allophanate
  • biurets such as biuret, dimethyl biuret, and tetramethyl biuret
  • L-ascorbic acid and its salts Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, and oxides of lan
  • the inkjet textile printing ink of the present invention can be produced by producing an aqueous pigment dispersion containing a pigment at a high concentration, and mixing the aqueous pigment dispersion with a polyether-based urethane resin as a binder resin, and, as necessary, other binder resins, an aqueous medium, a surfactant, and additives.
  • Examples of methods for producing the aqueous pigment dispersion include the following methods (1) to (3).
  • an organic solvent compatible with water such as methyl ethyl ketone or tetrahydrofuran, and the like
  • the kneading machine is not particularly limited, but examples include a Henschel mixer, a pressure kneader, a Banbury mixer, an intensive mixer, a planetary mixer, and a butterfly mixer.
  • ultrasonic homogenizers for example, ultrasonic homogenizers, high-pressure homogenizers, paint shakers, ball mills, roll mills, sand mills, sand grinders, Dyno Mills, Dispermats, SC Mills, Nanomizers, etc. can be used alone or in combination of two or more types.
  • the aqueous pigment dispersion preferably contains 5% to 60% by mass of pigment based on the total amount of the aqueous pigment dispersion in order to obtain an ink capable of producing printed matter with high image density and excellent dispersion stability, and it is even more preferable to use an aqueous pigment dispersion containing 10% to 50% by mass of pigment.
  • aqueous pigment dispersion since coarse particles contained in the aqueous pigment dispersion can cause deterioration of image characteristics, it is preferable to use an aqueous pigment dispersion from which coarse particles have been removed by centrifugation or filtration before or after producing the ink.
  • the dispersion process may be followed by an impurity removal process using ion exchange or ultrafiltration, followed by post-treatment.
  • Ion exchange can remove ionic substances such as cations and anions (divalent metal ions, etc.), and ultrafiltration can remove dissolved impurities (residual substances from pigment synthesis, excess components in the dispersion liquid composition, resins not adsorbed to organic pigments, contaminants, etc.).
  • a known ion exchange resin is used for the ion exchange process.
  • a known ultrafiltration membrane is used for the ultrafiltration process, and either a normal type or a type with double capacity can be used.
  • Methods for mixing the aqueous pigment dispersion obtained by the above method with the polyether-based urethane resin, etc. include, for example, a method of producing a mixture of the aqueous dispersion of the polyether-based urethane resin, etc. in advance, and mixing the mixture with the aqueous pigment dispersion, and a method of mixing the aqueous pigment dispersion with the aqueous dispersion of the polyether-based urethane resin, and then further mixing other additives such as a surfactant.
  • the mass ratio of the pigment to the total amount of the ink is preferably 1% by mass to 20% by mass in order to obtain sufficient image density and ensure good dispersion stability of the pigment in the ink.
  • the pH of the ink is preferably 7.0 or more, more preferably 7.5 or more, and even more preferably 8.0 or more, in order to improve the storage stability and ejection stability of the ink, and to improve the wetting spread, print density, and waterfastness when printed on a fabric that is easily or poorly ink-absorbent.
  • the upper limit of the pH of the ink is preferably 11.0 or less, more preferably 10.0 or less, and even more preferably 9.5 or less, in order to suppress deterioration of the components that constitute the ink application or ejection device (e.g., ink ejection port, ink flow path, etc.) and to reduce the effects of the ink coming into contact with the skin.
  • the inkjet textile printing ink of the present invention can be used, for example, in a printing method using an ink circulation type inkjet head.
  • An example of a printing device equipped with the ink circulation type inkjet head is a printing device equipped with a head having an ink circulation structure that has an ink inflow path and an ink outflow path in addition to the ink ejection nozzle, and the ink flowing out from the outflow path passes through the inflow path and is supplied back to the inkjet head.
  • a printing device equipped with a filter in the middle of the circulation structure can be preferably used.
  • the filter preferably has a pore size in the range of 5 ⁇ m to 20 ⁇ m, and it is preferable to use a filter with a pore size in the range of 5 ⁇ m to 10 ⁇ m in order to effectively remove foreign matter that may occur near the nozzle.
  • the ink tank that supplies the ink is not particularly limited, but may be a plastic bottle or a pouch-type ink bag. Also, an ink tank or ink bag with a circulation function may be used.
  • Examples of recording media that can be used when producing printed matter using the inkjet textile printing ink of the present invention and the printing method or printing device described above include fabrics and film substrates.
  • the above-mentioned fabric generally means a woven material made by alternately weaving threads made of fibers such as cotton in the vertical and horizontal directions.
  • the inkjet printing ink of the present invention is suitable not only for fabrics in the general sense, but also for media made of fibers such as nonwoven fabrics and knitted fabrics.
  • the material may be fabrics made of any natural or synthetic fibers such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, rayon, etc., or fabrics made of a blend of these fibers.
  • a printing device equipped with an ink-circulating inkjet head is used to print the inkjet textile printing ink of the present invention on the fabric.
  • the shortest distance between the ink ejection port of the ink circulation type inkjet head and the fabric is preferably set to 1 mm or more.
  • the shortest distance is more preferably set to 2 mm or more, and can also be set to 3 mm or more, in order to prevent contact between the surface of the fabric (recording surface) and the ink ejection port even if the fabric is highly fuzzed or uneven, and to effectively prevent damage to the ink ejection port and ink ejection failure caused by a decrease in the water repellency function that the ink ejection port often has.
  • the upper limit of the distance is preferably 10 mm or less, and more preferably 5 mm or less, in order to produce a printed matter without streaks.
  • the shortest distance may be the distance (gap) from a surface (x) having ink ejection ports of the inkjet head to a position (y) where a perpendicular line to the surface (x) (a perpendicular line assumed to the surface (x)) intersects with the fabric.
  • the lower limit of the size of the ink droplets when ejected from the ink circulation type inkjet head is preferably 10 pl, more preferably 15 pl, and even more preferably 20 pl, and the upper limit is preferably 50 pl, more preferably 45 pl, and even more preferably 40 pl, which is preferable in order to produce printed matter with excellent image quality without streaks and to obtain printed matter with even better washability.
  • a printed matter obtained by printing the ink of the present invention on a film substrate is called a transfer film
  • a printed matter printed on a fabric can be obtained by overlapping the receiving surface of the fabric with the printed surface of the transfer film and performing thermal transfer.
  • a method for producing a printed matter of the present invention includes a step of printing the ink for ink-jet textile printing of the present invention on a film substrate to obtain a transfer film, and a step of overlapping the receiving surface of the fabric with the printed surface of the transfer film and performing thermal transfer.
  • the film substrate may be a known film substrate for transfer used in transfer printing methods for fabrics.
  • the film substrate may be a single-layer structure consisting of a base film only, or may be a multilayer film having other layers formed on the base film.
  • the film substrate is preferably a multilayer film having a base film and a release layer.
  • base films include polyolefin-based films such as polypropylene film, polyethylene film, and polypropylene film; polyester-based films such as polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film; cellulose-based films such as diacetyl cellulose film and triacetyl cellulose film; polyurethane-based films; polyamide-based films; polyimide-based films; polyacrylate-based films; polymethacrylate-based films; and resin films such as polycarbonate-based films.
  • Polyolefin-based films and polyurethane-based films are preferred because the films conform to the unevenness of the mesh of the fibers of the fabric and provide high fixation.
  • the film substrate contains a polyester-based film, a polyolefin-based film, or a polyurethane-based film.
  • the release layer may be the same as the release layer of a known multi-layered transfer film.
  • the release layer may be a silicone layer or a non-silicone layer, and is not particularly limited.
  • Methods for forming the release layer on the base film include, but are not particularly limited to, coating and lamination.
  • the film substrate When the film substrate has a multi-layer structure, it may have layers other than the base film and the release layer. Examples of such layers include an antistatic treatment layer.
  • the inkjet printing ink can be ejected onto the film substrate by an inkjet method using an inkjet recording device to obtain a transfer film.
  • an inkjet recording device a known inkjet recording device may be used, and examples of the inkjet recording device include inkjet recording devices equipped with inkjet heads of continuous ejection type (charge control type, spray type, etc.) and on-demand type (piezo type, thermal type, electrostatic suction type, etc.).
  • inkjet recording device that uses an ink circulation type inkjet head.
  • the shortest distance between the ink ejection port of the ink circulation type inkjet head and the fabric is set to 0.5 mm or more.
  • the film substrate has little fuzz or unevenness, so it is more important to prevent contact between the recording surface and the ink ejection port and to produce a printed matter without streaks than to effectively prevent damage to the ink ejection port or ink ejection failure caused by a decrease in the water repellent function that the ink ejection port often has. Therefore, the upper limit of the distance is preferably 5 mm or less, and more preferably 3 mm or less.
  • the lower limit of the distance is not particularly limited, but is more preferably 0.8 mm or more, and even more preferably 1 mm or more.
  • the inkjet textile printing ink may be dried on the film substrate. For example, this can be done by heating the ejected inkjet textile printing ink using a heating device such as a heater, hot plate, oven, hot air dryer, or near infrared light. If the water-soluble solvent contained in the inkjet textile printing ink remains in the printing layer, the remaining solvent may volatilize when the transfer film is heated for transfer to the transfer target, resulting in a decrease in transfer quality. Therefore, the drying temperature is preferably 80°C or higher and 160°C or lower, and more preferably 100°C or higher and 150°C or lower. The drying time may be set appropriately depending on the drying temperature, and is, for example, 1 minute or higher and 10 minutes or lower.
  • the ink of the present invention can be inkjet printed onto a film substrate to form a transfer film, and the printed surface of the resulting transfer film can be overlaid on the surface of the fabric to be transferred, followed by a process of thermal transfer (sometimes referred to as the thermal transfer process) to obtain a printed material of the present invention.
  • a process of thermal transfer sometimes referred to as the thermal transfer process
  • the surface of the fabric to which the image is to be transferred may be subjected to a pretreatment step for improving transferability and fixability.
  • the pretreatment step may be, for example, a step of applying water or a pretreatment agent by spraying, using a coater, inkjet, or the like.
  • Thermal transfer refers to applying pressure while heating, and can be carried out by a known thermal transfer method.
  • a thermal transfer device a heat press device or the like can be used.
  • the heating temperature is not particularly limited as long as the printing layer can be transferred, and is, for example, 125°C or higher, preferably 130°C or higher.
  • the heating temperature is lower than the melting point of the film substrate of the transfer film, and is, for example, 200°C or lower, preferably 185°C or lower.
  • the film substrate can be made to follow the unevenness of the mesh of the fibers of the fabric, which is advantageous because it can improve the fixation of the transferred printing layer to the fabric.
  • the pressure is not particularly limited as long as the printing layer can be transferred, and is, for example, 100 g/cm2 or more and 10,000 g/cm2 or less, and preferably 200 g/cm2 or more and 5,000 g/cm2 or less .
  • the pressurization time is not particularly limited as long as the printing layer can be transferred, and is, for example, 3 seconds or more and 5 minutes or less, and preferably 5 seconds or more and 1 minute or less.
  • the method for producing the printed matter of the present invention may, and preferably, include a step of applying an adhesive resin to the printed surface of the transfer film prior to the thermal transfer step. This process applies the adhesive resin only to the printed areas of the transfer film, and then the adhesive resin melts through thermal transfer to bond the fabric and the printed surface, thereby making the fixation of the printed surface stronger.
  • the adhesive resin is not particularly limited and may be any known resin, for example, one containing polyester polyurethane as a main component.
  • the adhesive resin may also contain additives such as wax.
  • additives such as wax.
  • various commercially available products sold under the names of hot melt powder, hot melt binder, heat powder, transfer powder, DTF heat powder, DTF powder, etc. can be used.
  • not only white adhesive resin but also black colored adhesive resin can be used.
  • the adhesive resin may be a liquid or a powder, but is preferably a powder (powder-like). If the adhesive resin is a powder, the adhesive resin adheres only to the printing surface by applying it, without the inkjet textile printing ink having to be dried sufficiently on the film substrate. This allows only the necessary amount of adhesive resin to be used, and also reduces the energy and process required to dry the inkjet textile printing ink.
  • the adhesive resin can be applied by any known application method without any particular limitations.
  • adhesive resin powder can be sprinkled manually on each print.
  • DTF shaker adheresive resin applicator
  • the method for producing a printed matter of the present invention may include other processes.
  • Such other processes include, for example, a pre-treatment process, a post-treatment process, a drying process, etc., but are not limited to these.
  • the ink-jet textile printing ink of the present invention is applied to a polyethylene terephthalate plate and dried to produce a coating film having a thickness of 15 ⁇ m, the difference between the indentation depth at 100° C. and the indentation depth at 30° C. being less than 250 nm.
  • the indentation depth refers to the value measured by an ultra-microindentation hardness tester ENT-5 (manufactured by Elionix) to see how deep the test indenter is indented when a constant load is applied. Specifically, it refers to the indentation depth (unit: nm) measured under the following conditions. The deeper the indentation depth, the softer the coating film.
  • Measuring device Cho Micro Indentation Hardness Tester ENT-5 (manufactured by Elionix) Sample: Prepare a sample by applying the inkjet printing ink to a polyethylene terephthalate plate by spin coating to a film thickness of 15 ⁇ m, and drying for 15 minutes in an oven at 130° C. The temperature is adjusted to 30° C. and 100° C. before measurement.
  • the difference in indentation depth, H ⁇ L is less than 250 nm.
  • the difference in indentation depth H-L being less than 250 nm means that there is no significant difference between the indentation depth at 100° C. and the indentation depth at 30° C.
  • the ink of the present invention has a value of the difference in indentation depth H-L of less than 250 nm, preferably less than 200 nm, more preferably less than 180 nm, and even more preferably less than 100 nm.
  • the value of the difference in indentation depth H-L is within this range, the ink coating on the fabric is less likely to crack due to stretching, the coating thickness is uniform, and the color density (whiteness in the case of white ink) is improved.
  • the textile print of the present invention is a print in which the ink of the present invention is printed on a fabric, and more specifically, a textile print in which an ink for inkjet textile printing containing a pigment and a binder resin is printed on a fabric, wherein the binder resin is a polyether-based urethane resin, and the ink is an ink in which the difference in indentation depth between 100°C and 30°C of a coating film having a thickness of 15 ⁇ m that is applied to a polyethylene terephthalate plate and dried is less than 250 nm.
  • the printed textile product is suitable for use as a printed textile product, particularly for T-shirts, etc., since the ink follows the fabric even when the fabric is stretched and the printed textile product is unlikely to crack.
  • the printed textile product can also be used for other printed textile products, such as clothing, leather, decorative items, scarves, wrapping cloths, saris, curtains, bedding, tablecloths, embroidery thread, stuffed toys, novelty goods, flags, banners, etc., and is preferably printed textile products printed on substrates that are particularly easy to stretch in order to achieve the effects of the present invention.
  • Binder resin (Preparation of binder resin) ⁇ Production of Binder Resin 1>
  • a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1000 parts by mass of polytetramethylene ether glycol (number average molecular weight 3000), 314 parts by mass of dicyclohexylmethane diisocyanate, and then 0.1 parts by mass of stannous octylate were added, and the mixture was reacted at 100° C.
  • binder resin 1 containing a polyether-based urethane resin having a nonvolatile content of 35 mass % and a weight average molecular weight of 270,000, an acid value of 20 mgKOH/g, and a glass transition temperature of ⁇ 82° C., in which the urethane resin was dispersed in an aqueous medium.
  • the flow initiation temperature of binder resin 1 was 183° C.
  • ⁇ Production of binder resin 2> In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,000 parts by mass of polytetramethylene ether glycol (number average molecular weight 2000) and 412 parts by mass of methyl ethyl ketone were added and uniformly stirred, and then 141 parts by mass of dicyclohexylmethane diisocyanate and 0.1 parts by mass of stannous octylate were added and reacted for about 3 hours at 70° C.
  • 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, thereby obtaining a binder resin 2 containing a polyether-based urethane resin having a weight average molecular weight of 50,000, an acid value of 11 mgKOH/g, a glass transition temperature of -77°C, and a non-volatile content of 35% by weight in which the urethane resin was dispersed in an aqueous medium.
  • the flow initiation temperature of the binder resin 2 was 185°C.
  • Neorez R-967 manufactured by DSM, which is a polyether-based urethane resin, was used.
  • Binder Resin 4 In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 500 parts by mass of polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol with methyl carbonate, 500 parts by mass of polytetramethylene ether glycol (number average molecular weight 2000), 90 parts by mass of 2,2-dimethylolpropionic acid, and 643 parts by mass of methyl ethyl ketone were added, 411 parts by mass of dicyclohexylmethane diisocyanate was added, and then 0.1 parts by mass of stannous octylate was added, and the mixture was reacted at 80° C.
  • polycarbonate polyol number average molecular weight 2000
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end After dilution with 584 parts by weight of methyl ethyl ketone, 81 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above, and the carboxyl group in the urethane prepolymer was neutralized, and then 3831 parts by mass of water was added. Next, 22 parts by mass of an 80% by mass aqueous solution of hydrazine was added and reacted.
  • Binder Resin 4 which contains a polycarbonate polyether-based urethane resin having a weight average molecular weight of 334,000, an acid value of 25 mgKOH/g, a glass transition temperature of ⁇ 23° C., and a non-volatile content of 35% by mass in which the urethane resin was dispersed in an aqueous medium.
  • the flow initiation temperature of Binder Resin 4 was 147° C.
  • Binder Resin 5 In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,000 parts by mass of polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol with methyl carbonate, 50 parts by mass of dimethylolpropionic acid, and 730 parts by mass of methyl ethyl ketone were added and mixed uniformly, and then 306 parts by mass of dicyclohexylmethane diisocyanate was added, followed by 0.1 parts by mass of stannous octylate, and the mixture was reacted at 70° C.
  • polycarbonate polyol number average molecular weight 2000
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end 39 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained by the above method to neutralize the carboxyl group in the urethane prepolymer, and then 3993 parts by mass of ion-exchanged water was added, followed by adding 45 parts by mass of isophorone diamine to react. After the reaction was completed, methyl ethyl ketone was removed under reduced pressure at a temperature of 40° C.
  • Binder Resin 5 which contains a polycarbonate-based urethane resin having a nonvolatile content of 35 mass % and a weight average molecular weight of 330,000, an acid value of 15 mgKOH/g, and a glass transition temperature of ⁇ 20° C., in which the urethane resin was dispersed in an aqueous medium.
  • the flow initiation temperature of Binder Resin 5 was 152° C.
  • Binder Resin 6 In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1000 parts by mass of polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol with methyl carbonate, 78 parts by mass of 2,2-dimethylolpropionic acid, and 600 parts by mass of methyl ethyl ketone were added, followed by adding 0.1 parts by mass of stannous octylate, and reacting at 80° C.
  • polycarbonate polyol number average molecular weight 2000
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end 62 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above to neutralize the carboxyl group in the urethane prepolymer, and then 3332 parts by mass of water was added. Then, 21 parts by mass of an 80% by mass aqueous hydrazine solution was added and reacted. After the reaction was completed, methyl ethyl ketone was removed under reduced pressure at a temperature of 40° C.
  • Binder Resin 6 which contains a polycarbonate-based urethane resin having a nonvolatile content of 35 mass % and a weight average molecular weight of 75,000, an acid value of 23 mgKOH/g, and a glass transition temperature of ⁇ 37° C., in which the urethane resin was dispersed in an aqueous medium.
  • the flow initiation temperature of Binder Resin 6 was 100° C.
  • binder resin 7 In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1000 parts by mass of polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol with methyl carbonate, 94 parts by mass of 2,2-dimethylolpropionic acid, and 650 parts by mass of methyl ethyl ketone were added, and then 0.1 parts by mass of stannous octylate was added, and the mixture was reacted at 80° C.
  • polycarbonate polyol number average molecular weight 2000
  • a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end 74 parts by mass of triethylamine was added to the methyl ethyl ketone solution of the urethane prepolymer obtained above to neutralize the carboxyl group in the urethane prepolymer, and then 3610 parts by mass of water was added. Then, 23 parts by mass of an 80% aqueous hydrazine solution was added and the mixture was reacted. After the reaction was completed, methyl ethyl ketone was removed under reduced pressure at a temperature of 40° C.
  • Binder Resin 7 which contains a polycarbonate-based urethane resin having a nonvolatile content of 35 mass % in an aqueous medium, a weight average molecular weight of 202,000, an acid value of 26 mgKOH/g, and a glass transition temperature of ⁇ 27° C.
  • the flow initiation temperature of Binder Resin 7 was 164° C.
  • the binder resin 8 had a glass transition temperature of -31°C and a flow initiation temperature of 95°C.
  • Neorez R-600 manufactured by DSM
  • DSM polyether-based urethane resin
  • Binder resin 10 As the binder resin 10, M-141 (manufactured by Seiko PMC Corporation), which is an acrylic resin, was used.
  • the polymer obtained in the above process was transferred to the T-shaped micromixer M2 through the tube reactor R1 shown in Figure 1, and the growing end of the polymer was trapped by the reaction modifier ( ⁇ -methylstyrene ( ⁇ -MeSt)) introduced from the tube reactor P3.
  • the reaction modifier ⁇ -methylstyrene ( ⁇ -MeSt)
  • PA-1 block copolymer
  • the reaction temperature was set to 24°C by immersing the entire microreactor shown in Figure 1 in a thermostatic chamber.
  • the resulting block copolymer (PA-1) composition was hydrolyzed by treatment with a cation exchange resin, then distilled under reduced pressure, and the resulting solid was pulverized to obtain polymer E, a powdered dispersion aid with a weight average molecular weight of 2710 and an acid value of 145.
  • the powdered polymer (E) was 100% neutralized with KOH and used as an aqueous solution with a resin solid content of 15%.
  • Measurement device High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used, connected in series.
  • TKgel G5000 (7.8mm I.D. x 30cm) x 1 "TSKgel G4000” (7.8mm I.D. x 30cm) x 1 "TSKgel G3000” (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D. x 30cm) x 1
  • Detector RI (differential refractometer) Column temperature: 40°C Eluent: tetrahydrofuran (THF) Flow rate: 1.0 mL/min Injection volume: 100 ⁇ L (sample concentration 0.4% by mass in THF solution) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • Measurement was performed in accordance with JIS test method K 0070-1992. 0.5 g of a sample was dissolved in THF, and titrated with a 0.1 M alcoholic solution of potassium hydroxide using phenolphthalein as an indicator to determine the content.
  • the glass transition temperature was obtained by measuring each binder resin from which the dispersion medium had been completely removed using a differential scanning calorimeter (DSC) in accordance with JIS K 7121.
  • Example 1 An aqueous ink of Example 1 was obtained by mixing 35 parts by mass of the aqueous pigment dispersion (A1), 40.0 parts by mass of binder resin 1 (non-volatile content 35% by mass), 0.4 parts by mass of Surfynol 440 (manufactured by EVONIK, acetylene-based surfactant), 0.2 parts by mass of Surfynol 104PG50 (manufactured by EVONIK, acetylene-based surfactant), 2 parts by mass of glycerin, 10 parts by mass of ethylene glycol, 0.05 parts by mass of ACTICIDE B-20 (manufactured by Thor Japan Co., Ltd.) as a preservative, 1.7 parts by mass of a 15% by mass aqueous solution of Polymer E (100% neutralized with KOH), and the remainder as ion-exchanged water.
  • A1 aqueous pigment dispersion
  • binder resin 1 non-volatile content 35% by mass
  • Example 2 A water-based ink of Example 2 was obtained in the same manner as in Example 1, except that the binder resin of the ink was changed to the binder resin shown in Table 1.
  • Comparative Examples 1 to 8 Water-based inks of Comparative Examples 1 to 8 were obtained in the same manner as in Example 1, except that the binder resin of the ink was changed to the binder resin shown in Tables 2 and 3.
  • aqueous inks of Examples 1 and 2 and Comparative Examples 1 to 8 were spin-coated onto a polyester film substrate (Lumirror, manufactured by Toray), and then dried with hot air at 130° C. for 15 minutes to obtain a white ink coating film of about 15 ⁇ m.
  • the ink coating film obtained by the above method was subjected to measurement of indentation depth when a test indenter was pressed into the ink coating film at 100° C. or 30° C. with a load of 100 ⁇ N (load division number: 500, load step interval: 20 ms, load time: 10,000 ms) using an ultra-microindentation hardness tester ENT-5 (manufactured by Elionix).
  • the maximum indentation depth at 100° C. was defined as H (nm), and the maximum indentation depth at 30° C. was defined as L (nm), and the difference in indentation depth H-L was calculated and evaluated according to the following criteria.
  • the evaluation results are shown in Tables 1 to 3.
  • ⁇ The difference in indentation depth H-L is less than 250 nm.
  • ⁇ The difference in indentation depth H-L is 250 nm or more and less than 500 nm.
  • ⁇ The difference in indentation depth H-L is 500 nm or more and less than 800 nm.
  • XX The difference in indentation depth H-L is 800 nm or more.
  • the circulation filtration characteristics were evaluated by circulating 200 g of the aqueous inks obtained in the examples and comparative examples in a circulation device having a circulation path equipped with a SUS mesh filter with a pore size of 12 ⁇ m (manufactured by Manabe Kogyo Co., Ltd.) The flow rate of the aqueous ink immediately after the start of the circulation was adjusted to 50 g/min.
  • the flow rate of the aqueous ink was measured every hour from the start of the circulation, and the time when the flow rate became 25 g/min or less was recorded.
  • the circulation filterability was evaluated based on the following evaluation criteria. ⁇ : 120 hours or more from the start of circulation ⁇ : Less than 120 hours from the start of circulation
  • the aqueous ink obtained in the examples was solid-printed by inkjet ejection using a head manufactured by Seiko Epson Corporation onto a substrate film (Godora DTF transfer film-8.3 x 11.7) so that the film thickness after transfer was 15 ⁇ m, and the film was left to stand for 30 minutes to obtain a transfer film.
  • adhesive resin powder Europort DTF hot melt powder
  • the adhesive resin powder surface was heat-pressed against a black cotton knit at 140 ° C. for 5 seconds to obtain the textile prints of Examples 1 to 2 and Comparative Examples 1 to 8.
  • the product names and manufacturing company names in Tables 1 to 3 are as follows: The binder resin contents in Tables 1 to 3 are solid content values.
  • Surfynol 440 acetylene-based surfactant (manufactured by EVONIK)
  • Surfynol 104PG50 acetylene-based surfactant (manufactured by EVONIK)
  • ACTICIDE B-20 Preservative (manufactured by So Japan Co., Ltd.)
  • 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 pre-cooling 9: Tube reactor P3 for pre-cooling 10: Tube reactor P4 for pre-cooling

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
PCT/JP2024/020622 2023-06-22 2024-06-06 インクジェット用捺染インク及びインクジェット記録方法 Ceased WO2024262321A1 (ja)

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US20200087854A1 (en) * 2016-12-20 2020-03-19 Agfa Nv Method for ink jet textile printing
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JP2022085539A (ja) * 2020-11-27 2022-06-08 セイコーエプソン株式会社 インクセット及び記録方法
JP2022152286A (ja) * 2021-03-29 2022-10-12 セイコーエプソン株式会社 白色インクジェットインク組成物及びインクジェット記録方法

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Publication number Priority date Publication date Assignee Title
WO2008010396A1 (en) * 2006-07-20 2008-01-24 Konica Minolta Medical & Graphic, Inc. Actinic ray hardening ink and method of image forming, and inkjet recording apparatus, utilizing the ink
JP2018538387A (ja) * 2015-10-19 2018-12-27 コマート カンパニー リミテッドCommart Co., Ltd. インクジェットプリンタ用の繊維専用水性転写インク及びそれを適用するための繊維転写紙
US20200087854A1 (en) * 2016-12-20 2020-03-19 Agfa Nv Method for ink jet textile printing
JP2019002089A (ja) * 2017-06-15 2019-01-10 京セラドキュメントソリューションズ株式会社 転写捺染方法および捺染物
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