WO2019013265A1 - Encre pour jet d'encre, procédé d'impression à jet d'encre et tissu coloré - Google Patents

Encre pour jet d'encre, procédé d'impression à jet d'encre et tissu coloré Download PDF

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Publication number
WO2019013265A1
WO2019013265A1 PCT/JP2018/026223 JP2018026223W WO2019013265A1 WO 2019013265 A1 WO2019013265 A1 WO 2019013265A1 JP 2018026223 W JP2018026223 W JP 2018026223W WO 2019013265 A1 WO2019013265 A1 WO 2019013265A1
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Prior art keywords
dye
polymer
group
substituent
formula
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PCT/JP2018/026223
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English (en)
Japanese (ja)
Inventor
健太 牛島
藤江　賀彦
小林　博美
理俊 水村
誠 大元
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富士フイルム株式会社
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Publication of WO2019013265A1 publication Critical patent/WO2019013265A1/fr

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Classifications

    • 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
    • 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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • 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
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
    • 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
    • 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 an inkjet ink, an inkjet printing method, and a colored cloth.
  • An inkjet ink is an ink applicable to the inkjet method, and is widely used in various applications.
  • Ink-jet textile printing does not have to make a plate, can quickly form an image with excellent gradation, and uses only the amount of ink necessary for forming an image, so it has environmental advantages such as little waste liquid. It can be said that it is an excellent textile printing method.
  • Patent Document 1 describes sublimation transfer printing using an ink containing resin particles containing a disperse dye.
  • Patent Document 2 describes an ink jet printing method using an ink jet ink containing a pigment. In this method, a pigment and a surfactant as a dispersant are mixed in water, and then finely dispersed together with glass beads, zirconia beads, titania beads, or stainless steel balls by an attritor or milling machine, etc. It is done. Then, the colorant is diluted by a reducer blended with an emulsion resin for pigment fixation to prepare a pigment ink, and the pigment ink is adhered to a fiber by an ink jet system, and the pigment is adhered by fusing a resin by a heating roller. .
  • Patent Document 3 describes an inkjet ink containing a polymer having a specific structure in which a specific dye is linked to a polymer backbone.
  • Patent Documents 4 and 5 describe an ink containing an aqueous dispersion of polyurethane to which a colorant is bound.
  • Patent Document 1 can not form a clear image on fabrics other than polyester fabrics. That is, a property capable of forming a clear image (also referred to as "image clearness") is required for various types of fabrics.
  • image clearness also referred to as "image clearness”
  • the inkjet textile printing by the inkjet ink containing the pigment described in patent document 2 can not be said that the feel of the colored cloth obtained is excellent, and the wet rub fastness is also inferior.
  • Patent Documents 3 to 5 have no specific disclosure on crosslinking and printing, and neither describes the problems of image clarity, texture and wet rub fastness.
  • An object of the present invention is to provide an inkjet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an inkjet printing method using the above ink, and a colored cloth.
  • the inventors of the present invention have conducted intensive studies to solve the above problems, and an image clearness, feeling and wet friction are obtained by an inkjet ink containing an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure. It has been found that it is possible to provide an image with excellent fastness.
  • image sharpness, texture and texture are obtained by a method including the step of printing directly on a fabric by an inkjet method using an inkjet ink containing an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure. It was found that an image with excellent wet rub fastness was obtained.
  • the polymer having a structure derived from the dye contained in the inkjet ink is capable of coloring various types of fabrics.
  • the strength of the film formed by fusing the dye polymer is improved, and a colored cloth having excellent durability can be obtained. From this, it is considered that an image having excellent image clarity and texture and excellent in wet rub fastness can be provided.
  • the object of the present invention was specifically achieved by the following means.
  • An inkjet ink comprising an aqueous dispersion of a polymer having a structure derived from a dye and having a crosslinked structure.
  • the polymer containing at least one of a structure represented by the following general formula (1) and a structure represented by the following general formula (2) as a structure derived from the above dye, or a polymer represented by the following general formula (3
  • the inkjet ink according to [1] which is a polymer containing a structure represented by
  • X 1 and X 2 each independently represent -O-, -NH- or -NR 1- , R 1 represents a substituent, L 1 represents a trivalent linking group, L 2 represents a divalent linking group, and D 1 represents a dye residue obtained by removing any one hydrogen atom from the dye.
  • R 1 represents a substituent
  • L 1 represents a trivalent linking group
  • L 2 represents a divalent linking group
  • D 1 represents a dye residue obtained by removing any one hydrogen atom from the dye.
  • X 3 and X 4 each independently represent -O-, -NH- or -NR 1- , R 1 represents a substituent, and L 3 and L 4 each independently represent a single bond Or a divalent linking group, L 5 represents a divalent linking group, and D 2 represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye.
  • R 1 represents a substituent
  • L 3 and L 4 each independently represent a single bond Or a divalent linking group
  • L 5 represents a divalent linking group
  • D 2 represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye.
  • R 2 to R 4 each independently represent a hydrogen atom or a substituent
  • L 6 is a single bond or a divalent represented by the following formula (L6-1) or (L6-2)
  • D 1 represents a linking group
  • D 1 represents a dye residue obtained by removing one hydrogen atom from the dye.
  • L 7 represents a single bond or a divalent linking group
  • * 4 represents a position to be bonded to a carbon atom in General Formula (3)
  • * 5 is a general formula (3) Represents a position to bind to D 1 in
  • L 8 represents a single bond or a divalent linking group
  • * 6 represents a position to be bonded to a carbon atom in general formula (3)
  • * 7 represents a general formula (3) Represents a position to bind to D 1 in
  • D 1 of the above general formula (1), the general formula (2) Medium D 2, or D 1 of the above general formula (3) is selected from the group of the following formula (M1) ⁇ (M8)
  • the inkjet ink according to [2] which represents a dye residue obtained by removing one or two arbitrary hydrogen atoms from the dye represented by at least one.
  • R 101 to R 110 each independently represent a hydrogen atom or a substituent.
  • R 201 to R 215 each independently represent a hydrogen atom or a substituent, X 201 represents a monovalent anion, and n 201 represents 0 or 1.
  • R 301 to R 317 each independently represent a hydrogen atom or a substituent, X 301 represents a monovalent anion, and n 301 represents 0 or 1.
  • R 402 to R 407 each independently represent a hydrogen atom or a substituent
  • Ar 401 represents a phenyl group, a naphthyl group or a heterocyclic group, and the above phenyl group, the above naphthyl group or The above-mentioned heterocyclic group may further have a substituent
  • R 501 to R 508 each independently represent a hydrogen atom or a substituent.
  • R 601 to R 602 each independently represent a hydrogen atom or a substituent
  • R 603 represents a hydrogen atom or a substituent
  • Ar 601 represents a phenyl group, a naphthyl group or a heterocyclic group
  • the phenyl group, the naphthyl group or the heterocyclic group may further have a substituent.
  • R 701 to R 706 each independently represent a hydrogen atom or a substituent.
  • R 811 to R 818 and R 821 to R 828 each independently represent a hydrogen atom or a substituent.
  • [4] The inkjet ink according to any one of [1] to [3], wherein the average particle size of the polymer is 50 to 500 nm.
  • [5] The inkjet ink according to any one of [1] to [4], wherein the polymer is a urethane polymer.
  • [6] The inkjet ink according to any one of [1] to [4], wherein the polymer is an acrylic polymer.
  • An ink jet printing method comprising the step of printing directly on a fabric by an ink jet method using the ink jet ink according to any one of [1] to [8].
  • a colored cloth comprising a cloth and a polymer having a structure derived from a dye and having a crosslinked structure.
  • an object of the present invention to provide an ink jet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an ink jet printing method using the ink, and a colored cloth.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • “(meth) acrylate” represents at least one of acrylate and methacrylate
  • “(meth) acrylic” represents at least one of acrylic and methacrylic
  • “(meth) acryloyl” represents at least one of acryloyl and methacryloyl. Represents a kind.
  • the “substituent selected from Substituent Group A” refers to the substituents described in [0012] to [0051] of WO 2015/199135. Further, in the present specification, the substituent group A1 includes the following substituents.
  • Substituent group A1 A halogen atom, an alkyl group (preferably having a carbon number of 1 to 30), a cycloalkyl group (preferably having a carbon number of 3 to 30), an aryl group (preferably having a carbon number of 6 to 30), a heterocyclic group (preferably having a carbon number of 3 to 30) 30), an acyl group (preferably having a carbon number of 2 to 30), a hydroxyl group, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxy group (preferably having a carbon number of 1 to 30), and an aryloxy group (preferably having a carbon number of 6 to 30), an acyloxy group (preferably having a carbon number of 2 to 30), an alkoxycarbonyl group (preferably having a carbon number of 2 to 30), an aryloxycarbonyl group (preferably having a carbon number of 7 to 30), a carbamoyl group, a sulfam
  • an ionic group such as a sulfo group or a carboxyl group may be in a state including a cation or an anion (also referred to as a “salt state”).
  • a carboxyl group, a phosphate group, and a sulfo group may be in a state including a cation
  • examples of the cation forming a salt state include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion) Potassium ion) and organic cations (eg, tetramethyl ammonium ion, tetramethyl guanidinium ion, tetramethyl phosphonium).
  • the structure derived from a dye means any organic compound used as a dye. It is a group (dye residue) formed by removing one or more hydrogen atoms, and preferably a group formed by removing one or two arbitrary hydrogen atoms from an organic compound used as a dye.
  • the dye polymer is a dye multimer containing a structure derived from a dye, and is a reticulated polymer.
  • the method for obtaining the dye polymer is optional, but the monomer containing the structure derived from the dye (also referred to as "dye monomer”) is polymerized or copolymerized with other monomers to obtain the dye polymer.
  • the monomer containing the structure derived from the dye also referred to as "dye monomer”
  • the method for producing the dye polymer or the polymer having no structure derived from the dye is not particularly limited, but those synthesized by radical polymerization, addition polymerization or condensation polymerization are preferably used.
  • the structure derived from the dye may be any structure derived from the dye as classified by the color index (abbreviated as "CI"), or any substituent within the range that exerts the effect of the present invention on the structure. It is preferable that it is the structure which substituted, or the structure which remove
  • CI color index
  • dyes examples include azo dyes (monoazo dyes, disazo dyes, trisazo dyes, polyazo dyes), stilbene dyes, carotenoid dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes (monomethine) Dyes, polymethine dyes), azomethine dyes, aniline dyes, indoaniline dyes, indamine dyes, indophenol dyes, indophenol dyes, azine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, diglossin dyes, porphyrin dyes, dicyanostyryl dyes And dyes, cyanine dyes, and phthalocyanine dyes.
  • azo dyes monoazo dyes, disazo dyes, trisazo dyes, poly
  • the dye is an azo dye, stilbene dye, diarylmethane dye, triarylmethane dye, xanthene dye, acridine dye, quinoline dye, polymethine dye, monomethine dye, azomethine dye, indoaniline dye, indoline dye At least one dye selected from the group consisting of phenol dyes, nigrosine dyes, oxazine dyes, thiazine dyes, anthraquinone dyes, indigo dyes, quinophthalone dyes, porphyrin dyes, cyanine dyes and phthalocyanine dyes, more preferably azo dyes, Stilbene dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, indoaniline dyes, indophenol dyes, nigrosine dyes, anthraquinone dyes, quinophthalone dyes, and phthalocyani
  • the dye may be a dye that is soluble in water or a dye that is insoluble in water, but is a dye that is insoluble in water from the viewpoint of the water resistance and the wash resistance of the dye polymer. preferable. Moreover, it is preferable that it is a dye which does not have ionic groups, such as a carboxyl group, a sulfo group, a phosphoric acid group, these salts, and an ammonium group. Such a dye is not particularly limited. For example, a dye insoluble in water such as a disperse dye may be used, or a dye structure in which an ionic group is removed from a water-soluble dye may be used.
  • the dye polymer a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond, or a urethane polymer is preferably used.
  • an acrylic polymer, a vinyl polymer, or a styrene polymer is mentioned, for example.
  • the acrylic polymer in the present invention is a polymer having at least one repeating unit from the group consisting of repeating units derived from (meth) acrylic acid and repeating units derived from (meth) acrylic acid ester.
  • the styrene polymer in the present invention refers to a polymer having a repeating unit derived from styrene.
  • the urethane polymer (also referred to as "polyurethane”) in the present invention is a polymer having a urethane bond, and is formed by the polymerization reaction of a compound having two or more hydroxyl groups and a compound having two or more isocyanate groups. Ru.
  • an acrylic polymer or a urethane polymer is preferable.
  • a polymer containing at least one of a structure represented by the following general formula (1) and a structure represented by the following general formula (2) one or two of the structures represented by the following general formula (1) Polymers Containing Above, Polymers Containing One or Two or More Structures Represented by the Following General Formula (2), One or More Structures Contained by the Following General Formula (1), and the Following General Formula (2) Examples thereof include a polymer containing one or more of the structures represented, a polymer containing a structure represented by the following general formula (1) and at least one structure represented by the following general formula (2), and other structures.
  • a polymer containing a structure represented by the following general formula (3) a polymer containing one or two or more types of a structure represented by the following general formula (3), a
  • X 1 and X 2 each independently represent -O-, -NH- or -NR 1- , R 1 represents a substituent, L 1 represents a trivalent linking group, L 2 represents a divalent linking group, and D 1 represents a dye residue obtained by removing any one hydrogen atom from the dye.
  • R 1 represents a substituent
  • L 1 represents a trivalent linking group
  • L 2 represents a divalent linking group
  • D 1 represents a dye residue obtained by removing any one hydrogen atom from the dye.
  • X 3 and X 4 each independently represent -O-, -NH- or -NR 1- , R 1 represents a substituent, and L 3 and L 4 each independently represent a single bond Or a divalent linking group, L 5 represents a divalent linking group, and D 2 represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye.
  • R 1 represents a substituent
  • L 3 and L 4 each independently represent a single bond Or a divalent linking group
  • L 5 represents a divalent linking group
  • D 2 represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye.
  • R 2 to R 4 each independently represent a hydrogen atom or a substituent
  • L 6 is a single bond or a divalent represented by the following formula (L6-1) or (L6-2)
  • D 1 represents a linking group
  • D 1 represents a dye residue obtained by removing one hydrogen atom from the dye.
  • L 7 represents a single bond or a divalent linking group
  • * 4 represents a position to be bonded to a carbon atom in General Formula (3)
  • * 5 is a general formula (3) Represents a position to bind to D 1 in
  • L 8 represents a single bond or a divalent linking group
  • * 6 represents a position to be bonded to a carbon atom in general formula (3)
  • * 7 represents a general formula (3) Represents a position to bind to D 1 in
  • X 1 and X 2 each independently represent —O—, —NH— or —NR 1 —, and R 1 represents a substituent.
  • R 1 is preferably an alkyl group, a cycloalkyl group or an aryl group.
  • X 1 and X 2 preferably represent -O- or -NH-, more preferably -O-.
  • at least one of X 1 and X 2 represents -O-.
  • L 1 represents a trivalent linking group.
  • the trivalent linking group represented by L 1 is not particularly limited as long as the effects of the present invention can be exhibited. However, substituted or unsubstituted linear, branched or cyclic aliphatic hydrocarbon having 1 to 30 carbon atoms Group (which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group), a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms (even an aromatic hydrocarbon group) , An aromatic heterocyclic group), a linking group represented by the following general formula (L-1), a linking group represented by the following general formula (L-2), and two or more of these linking The linking group formed is preferred.
  • substituents in case these have a substituent, the substituent (The substituent selected preferably from said substituent group A1) chosen from said substituent group A is mentioned.
  • substituent group A1 chosen from said substituent group A is mentioned.
  • substituent group A1 chosen from said substituent group A is mentioned.
  • substituent group A1 chosen from said substituent group A is mentioned.
  • L 11 and L 12 each independently represent a single bond or a divalent linking group.
  • * 1 and * 2 each represent a position to be bonded to X 1 and X 2 in the general formula (1), and * 3 represents a position to be bonded to D 1 in the general formula (1).
  • L 11 and L 12 each independently represent a single bond or a divalent linking group.
  • L 2 represents a divalent linking group.
  • Examples of the divalent linking group represented by L 2 include divalent linking groups in the case where L 11 and L 12 in the general formulas (L-1) and (L-2) represent a divalent linking group. It is similar to that described in the description.
  • D 1 represents a dye residue obtained by removing one arbitrary hydrogen atom from the dye.
  • D 1 is not limited as long as the effects of the present invention can be exhibited, it represents a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by any one of the following formulas (M1) to (M8) Is preferred.
  • General formula (M2) and (M3) shall also contain each resonance structure.
  • R 101 to R 110 each independently represent a hydrogen atom or a substituent.
  • R 201 to R 215 each independently represent a hydrogen atom or a substituent, X 201 represents a monovalent anion, and n 201 represents 0 or 1.
  • R 301 to R 317 each independently represent a hydrogen atom or a substituent, X 301 represents a monovalent anion, and n 301 represents 0 or 1.
  • R 402 to R 407 each independently represent a hydrogen atom or a substituent
  • Ar 401 represents a phenyl group, a naphthyl group or a heterocyclic group, and the above phenyl group, the above naphthyl group or The above-mentioned heterocyclic group may further have a substituent
  • R 501 to R 508 each independently represent a hydrogen atom or a substituent.
  • R 601 to R 602 each independently represent a hydrogen atom or a substituent
  • R 603 represents a hydrogen atom or a substituent
  • Ar 601 represents a phenyl group, a naphthyl group or a heterocyclic group
  • the phenyl group, the naphthyl group or the heterocyclic group may further have a substituent.
  • R 701 to R 706 each independently represent a hydrogen atom or a substituent.
  • R 811 to R 818 and R 821 to R 828 each independently represent a hydrogen atom or a substituent.
  • General formula (M2) and (M3) shall also contain each resonance structure.
  • Examples of the substituent when 811 to R 818 and R 821 to R 828 represent a substituent include a substituent selected from the above-mentioned Substituent Group A (preferably, a substituent selected from the above Substituent Group A1).
  • R 501 to R 508 in the general formula (M5) and R 601 to R 602 in the general formula (M6) represent a substituent
  • at least two of the substituents are preferably bonded to each other 6-membered or 7-membered saturated ring or unsaturated ring may be formed.
  • the formed 5-, 6-, and 7-membered rings are further substitutable groups, they may further have a substituent, and the substituent is selected from Substituent Group A above. Included (preferably, a substituent selected from the above-mentioned Substituent Group A1).
  • the substituent when Ar 401 in General Formula (M4) further has a substituent and the substituent when Ar 601 in General Formula (M6) further has a substituent is selected from Substituent Group A above
  • the substituent preferably, a substituent selected from the above-mentioned substituent group A1 can be mentioned.
  • X 201 in the general formula (M2) and X 301 in the general formula (M3) preferably chlorine ion, acetate ion, triflate ion, tetrafluoroborate ion, tetrakis (pentafluorophenyl) borate ion, perchlorate ion, or Bis (trifluoromethanesulfonyl) imide anion is preferred.
  • the dyes represented by the above general formulas (M1) to (M8) may be classified by color index and may be synthesized by a conventionally known method (for example, Japanese Patent Publication No. 7-49583, Patent Patent Publication No. 5715380, International Publication No. WO 2010/110199, Japanese Patent Publication No. 2002-509957, etc.).
  • dyes represented by the above general formulas (M1) to (M8) are those described in [0126] to [0132] of PCT / JP 2017/002788, [0092] to [0092] of Japanese Patent Application No. 2017-034066. Reference can be made to those described in [0100] and those described in [0068] of JP-A-2013-535558.
  • X 3 and X 4 in the general formula (2) have the same meanings as X 1 and X 2 in the general formula (1), and the preferred range is also the same.
  • L 3 and L 4 each independently represent a single bond or a divalent linking group
  • L 5 represents a divalent linking group.
  • Examples of the divalent linking group when L 3 and L 4 represent a divalent linking group, and the divalent linking group represented by L 5 include the groups represented by general formulas (L-1) and (L-2) described above. Are the same as described in the description of the divalent linking group when L 11 and L 12 in the above each represent a divalent linking group.
  • L 3 and L 4 preferably represent a single bond.
  • D 2 represents a dye residue obtained by removing two arbitrary hydrogen atoms from the dye.
  • D 2 is not limited as long as the effects of the present invention can be obtained, but a dye residue obtained by removing two arbitrary hydrogen atoms from the dye represented by any one of the general formulas (M1) to (M8) is It is further preferable to represent.
  • preferred ranges and specific examples of the general formulas (M1) to (M8) are the same as those described above.
  • the dye polymer in the present invention is a polyurethane having a structure derived from a dye, typically, a compound having two or more hydroxyl groups such as diol or triol which is a monomer, and diisocyanate which is a monomer Etc. is synthesized by polymerization reaction with a compound (polyisocyanate compound) having two or more isocyanate groups such as, but as is also apparent from the structure represented by the above general formula (1) or (2), it is not limited thereto. Obtained by the polymerization reaction of a monomer having a total of two or more groups selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group, and a monomer having two or more isocyanate groups.
  • the dye polymer in the present invention is a polyurethane, it has a structure derived from the dye and is a single substance having a total of two or more groups selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group. It is preferable to have a structure formed by polymerizing a monomer (dye monomer) and a monomer having two or more isocyanate groups.
  • the number of the groups selected from the group consisting of the hydroxyl group, the primary amino group and the secondary amino group is the number of those which can react with the isocyanate group in consideration of steric hindrance and the like.
  • the aforementioned dye (preferably a dye represented by any one of the general formulas (M1) to (M8)) comprises a total of 2 groups selected from the group consisting of a hydroxyl group, a primary amino group and a secondary amino group. When it has one or more, it can be used as a dye monomer. Moreover, when the above-mentioned dye (preferably a dye represented by any of the general formulas (M1) to (M8)) does not have a hydroxyl group, a primary amino group or a secondary amino group, hydroxyl is used as the dye.
  • a dye monomer can be obtained by introducing a group, a primary amino group or a secondary amino group by a chemical reaction.
  • the polymer containing the structure represented by the general formula (3) is preferably a vinyl polymer, an acrylic polymer or a styrene polymer.
  • R 2 and R 3 in the general formula (3) each independently represent a hydrogen atom or a substituent, and as a substituent when representing a substituent, a substituent selected from the above-mentioned Substituent Group A (preferably the above-mentioned Substituents selected from Substituent Group A1) can be mentioned.
  • R 2 and R 3 preferably represent a hydrogen atom.
  • R 4 in the general formula (3) represents a hydrogen atom or a substituent, and a substituent selected from the above-mentioned Substituent group A (preferably selected from the above-mentioned Substituent group A1) as a substituent when representing a substituent Substituent)).
  • R 4 preferably represents a hydrogen atom or a methyl group.
  • Each of L 7 in the above formula (L 6-1) and L 8 in the above formula (L 6-2) independently represents a single bond or a divalent linking group, and in the case of a divalent linking group,
  • the linking group is the same as that described in the description of the divalent linking group in the case where L 11 and L 12 in the general formulas (L-1) and (L-2) above represent a divalent linking group. It is.
  • L 6 in the general formula (3) represents a divalent linking group represented by the above formula (L6-1).
  • D 1 represents a dye residue obtained by removing an arbitrary hydrogen atom from the dye.
  • D 1 is not limited as long as the effects of the present invention can be exhibited, but a dye residue obtained by removing one arbitrary hydrogen atom from the dye represented by any one of the general formulas (M1) to (M8) is It is further preferable to represent. Also in D 1 of the general formula (3), preferred ranges and specific examples of the general formulas (M1) to (M8) are the same as described above.
  • the dye polymer is a polymer having a structure derived from a dye and having a crosslinked structure.
  • the crosslinked structure refers to a compound having two or more ethylenically unsaturated bonds in the molecule as at least one monomer in the case of a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond. It represents a structure obtained by polymerization.
  • a crosslinked structure represents the structure obtained by using the compound which has a hydroxyl group and an isocyanate group three or more in total in a molecule
  • numerator as at least one monomer.
  • Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol (meth) acrylate Etc.
  • Examples of compounds having a total of three or more hydroxyl groups and isocyanate groups in the molecule include compounds having a total of three or more hydroxyl groups in the molecule or compounds having a total of three or more isocyanate groups in the molecule. .
  • Examples of the compounds having a total of three or more hydroxyl groups in the above molecule include glycerin, polyglycerin, trimethylolpropane, pentaerythritol and the like.
  • Examples of the compound having a total of three or more isocyanate groups in the molecule described above include polymeric MDI, duranate (manufactured by Asahi Kasei Corp., trade name), and the like.
  • numerator is preferable.
  • the presence or absence of the crosslinked structure of the dye polymer can be judged by the solubility of the dye polymer.
  • An aqueous dispersion containing the dye polymer of the present invention or an inkjet ink is mixed with various solvents such as dimethyl sulfoxide (DMSO), N-methyl pyrrolidone (NMP), tetrahydrofuran and the like, and in any case it has a crosslinked structure It can be judged to be a gel. If it can not be determined visually, it is filtered through a filter of the average particle size of the aqueous dispersion, or if the particle size can be observed by particle size measurement, it is judged to be a gel having a crosslinked structure. it can. Alternatively, it can be determined by measuring the gel fraction in accordance with JIS Standard 6769.
  • the dye polymer in the present invention has a structure derived from the dye and a compound having one or more ethylenically unsaturated bonds (dye It is preferable that it is a polymer obtained by polymerizing a monomer).
  • the aforementioned dye preferably a dye represented by any of the general formulas (M1) to (M8)
  • M1 to (M8) has an ethylenically unsaturated bond
  • the dye when the aforementioned dye (preferably a dye represented by any of the general formulas (M1) to (M8)) does not have an ethylenically unsaturated bond, the dye chemically reacts with the ethylenically unsaturated bond.
  • the dye monomer can be obtained by introducing
  • the polyisocyanate compound is a compound having two or more isocyanate groups in one molecule, and in the present invention, a compound having two isocyanate groups in one molecule is preferable.
  • Examples of polyisocyanate compounds include phenylene diisocyanate, cyclohexane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, It is possible to use norbornene diisocyanate, lysine diisocyanate, an oligomer of the above diisocyanate, and a reaction product of 1 mole of diol and 2
  • a catalyst can be used in the reaction of the dye monomer and the polyisocyanate compound.
  • the catalyst tin compounds, titanium compounds, bismuth compounds, zinc compounds, organic bases (tertiary amine compounds, or diazabicycloundecene (DBU) and the like) can be suitably used.
  • the dye polymer may have a structure other than the structure derived from the dye.
  • the dye polymer is a polymer obtained by polymerizing a monomer having an ethylenically unsaturated bond
  • the dye polymer in the present invention is a polyurethane
  • it may be a polymer obtained by reacting the above-mentioned dye monomer and another monomer other than the polyisocyanate compound.
  • a diol is preferable. Further, diols having a carboxyl group are also preferred.
  • the dye polymer in the present invention may have a soft segment to improve the quality (feel) and the fastness of the colored cloth.
  • the soft segment can be introduced into the dye polymer by copolymerizing the corresponding diol compound or diamine compound. These may be used alone or in combination of two or more.
  • Diol compounds which can be used for the introduction of the soft segment include polyethylene glycol diol, polypropylene glycol diol, polytetramethylene oxide, polyester diol, polycaprolactone diol, polycarbonate diol, polybutadiene diol, polyisoprene diol, hydrogenated polybutadiene diol, Hydrogenated polyisoprene diol and polydimethylsiloxane diol can be preferably used.
  • the polyester diol is preferably a compound obtained by condensing a dibasic acid such as adipic acid or isophthalic acid with an alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol or 1,6-hexanediol.
  • the polycaprolactone diol is preferably a compound obtained by ring-opening polymerization of caprolactone from ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol or the like.
  • diol compound that can be used for soft segment introduction polyethylene glycol diol, polypropylene glycol diol, polytetramethylene oxide, polyester diol, polycaprolactone diol, and polycarbonate diol are more preferable.
  • the diamine compound that can be used for the introduction of the soft segment is preferably polyethylene glycol diamine or polypropylene glycol diamine.
  • the dye polymer in the present invention when it is a polyurethane, it may further have a urea bond.
  • a polymer having a urethane bond and a urea bond is also called "polyurethane / urea".
  • a polyurethane / urea in which a structure derived from a dye and a first partial structure containing a urethane bond and a second partial structure containing a urethane bond are linked by a urea bond. It can be mentioned.
  • the aqueous dispersion of dye polymer contains at least water and dye polymer, and the dye polymer is dispersed in water.
  • the dye polymer water dispersion may contain an aqueous organic solvent.
  • the low molecular weight surfactant or the high molecular weight dispersant may be used in combination or may not be used in combination (so-called self-dispersion).
  • the dye polymer may be used alone or in combination of two or more at any ratio.
  • the above-mentioned dye polymer is used in the state of being dispersed in water, not in the state of being dissolved in water.
  • the dye polymer In a state where the dye polymer is dispersed in water, it is a polymer substantially insoluble in water, unlike a state in which it is dissolved in water, so that it is excellent in water resistance such as washing resistance and sweat resistance.
  • the dye polymer In the ink jet printing method of the present invention, the dye polymer is a substantially water-insoluble polymer because the step of washing with water after printing is unnecessary.
  • the dye polymer insoluble in water is dispersed as particles, and its average particle size is preferably 50 to 500 nm.
  • the dye polymer When the dye polymer is soluble in water, the dye polymer is not present as particles in water. It is preferable to use ultrapure water as water.
  • the dye polymer when dispersed in water, is easy to be compatible with water (wettable) or electrostatic repulsion (repulsive force) as a property of the dye polymer itself or by adsorption with a low molecular type surfactant or a polymer type dispersant used in combination. Or steric repulsion to prevent reaggregation of the fine particles of the dye polymer, and has the function of suppressing sedimentation.
  • the dye polymer is in the form of particles in the aqueous dispersion.
  • the average particle size of the particulate dye polymer in the aqueous dispersion of the dye polymer is preferably 50 to 500 nm, more preferably 50 to 300 nm, and particularly preferably 50 to 200 nm. Within this range, the fabric can be printed by the inkjet method.
  • the average particle diameter in this specification used the value measured using the particle size distribution measuring apparatus (Nanotrac UPA EX150, the Nikkiso Co., Ltd. make, brand name).
  • the content of the dye polymer in the dye polymer aqueous dispersion is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass. If it is in this range, it is possible to obtain a colored cloth with high density in printing while securing the storage stability as an inkjet ink.
  • the content of water in the dye polymer aqueous dispersion is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and particularly preferably 60 to 90% by mass. Within this range, the stability of the dye-polymer water dispersion and the ejection stability as an inkjet ink can be imparted, which is preferable. The stability of the dye-polymer water dispersion indicates that sedimentation and the like hardly occur.
  • the aqueous organic solvent is preferably 10 g / 100 g-H 2 O or more as water solubility at 25 ° C., more preferably 20 g / 100 g-H 2 O or more, and miscible with water at an arbitrary ratio Is particularly preferred.
  • the aqueous organic solvent include alcohol solvents, amide solvents, and nitrile solvents.
  • the content of the aqueous organic solvent in the dye polymer aqueous dispersion is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 10 to 30% by mass. Within this range, the stability of the dye-polymer water dispersion and the ejection stability as an inkjet ink can be imparted, which is preferable.
  • the low molecular weight surfactant or the high molecular weight dispersant is preferably a low molecular weight surfactant or a high molecular weight dispersant having a hydrophobic group and an ionic group, and is added when the dye polymer is dispersed.
  • Low-molecular-weight surfactant or high-molecular-weight dispersant adsorbs to the surface of the dye polymer and makes it wet (is wet) with water, and electrostatic repulsion (repulsion) or steric repulsion of dye polymer fine particles milled by mechanical action It prevents the reaggregation of fine particles and has the function of suppressing the formation of sedimentation.
  • the content of the low molecular weight surfactant is preferably in the range of 0.001 to 5.0% by mass with respect to the total mass of the dye-polymer aqueous dispersion, and the surface tension of the aqueous dispersion is arbitrarily selected in this range It is preferable to adjust to
  • the content of the polymer-type dispersant is preferably in the range of 0.001 to 50% by mass with respect to the total mass of the dye polymer water dispersion, and the surface tension of the water dispersion is arbitrarily adjusted in such a range It is preferable to do.
  • the method for producing the aqueous dispersion of the dye polymer is not particularly limited, and examples thereof include the methods shown in (i) to (v) below.
  • (I) A method of mixing the powder or paste of the crosslinked dye polymer in water and then finely dispersing it with an attritor or mill together with glass beads, zirconia beads, titania beads or stainless steel balls, etc.
  • the dye polymer is a polymer obtained by polymerizing a compound having an ethylenically unsaturated bond
  • a compound having two or more ethylenically unsaturated bonds in at least one of the monomers is a method of introducing a crosslinked structure into the dye polymer
  • the dye polymer is a polyurethane
  • it may be produced by using a trifunctional or higher functional polyisocyanate and / or a polyol and / or a polyamine for at least one of the monomers.
  • the method manufactured using the prepolymer of 3 or more functional groups in at least one of the prepolymer which has an isocyanate group at the terminal is mentioned.
  • the non-aqueous organic solvent is not an aqueous organic solvent among organic solvents, and preferably less than 10 g / 100 g-H 2 O as water solubility at 25 ° C.
  • glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, polyethylene glycol etc., and urea, hyaluronic acid, sucrose etc. are added to the aqueous dispersion of these dye polymers as required. can do.
  • nonionic surfactants or anionic surfactants can be added as dispersion aids, but these surfactants should be added in a small amount so as not to degrade the performance as dispersion stability. Is preferred.
  • the dye polymer water dispersion is used in the above-mentioned manner (a) because the amount of the precipitate is small, the dispersion stability is good, streaks and unevenness are less likely to occur when deposited by the ink jet method, and clear printed matter can be obtained.
  • Preferred is a method of preparing an inkjet ink using the dye polymer water dispersion produced by the method iv) or (v) and produced by these methods.
  • Ethyl acetate, methyl ethyl ketone, tetrahydrofuran and the like are preferable as the organic solvent in the above methods (iv) and (v).
  • the inkjet ink of the present invention contains at least an aqueous dispersion of dye polymer. That is, the inkjet ink of the present invention is a dispersion liquid in which a dye polymer is dispersed in a liquid containing water.
  • the dye polymer is in the form of particles, and the preferred average particle diameter of the dye polymer in the form of particles is the same as described above.
  • the ink jet ink may contain a crosslinking agent in order to improve the abrasion resistance or the washing fastness of the colored cloth.
  • a crosslinking agent examples include blocked isocyanate crosslinking agents (for example, Maycanate CX, TP-10, DM-35 HC, SU-268A, etc., all manufactured by Meisei Kogyo Co., Ltd., trade names) and polyfunctional epoxy crosslinking agents (for example, And Denacol EX-313, 314, 322, 411, etc., all of which are manufactured by Nagase ChemteX Co., Ltd. (trade names).
  • the inkjet ink of the present invention may contain other components other than those described above.
  • colorants other than the above dye polymers organic solvents, surfactants, pH adjusters, fluorescent brighteners, surface tension adjusters, antifoamers, anti-drying agents, lubricants, thickening agents
  • UV absorbers antifading agents, antistatic agents, matting agents, antioxidants, specific resistance regulators, rust inhibitors, inorganic pigments, reduction inhibitors, preservatives, fungicides, chelating agents, etc.
  • the content of the dye polymer in the inkjet ink is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 12% by mass.
  • the content of water in the inkjet ink is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 50 to 80% by mass.
  • the viscosity at 25 ° C. of the inkjet ink of the present invention is preferably 40 mPa ⁇ s or less, more preferably 1 to 30 mPa ⁇ s, and more preferably 2 to 20 mPa ⁇ s.
  • the viscosity at 25 ° C. of the inkjet ink can be measured, for example, by a commercially available vibration viscometer.
  • the preparation method of an inkjet ink is not specifically limited, For example, it can prepare by mixing the water dispersion liquid of a dye polymer, and water or other components as needed.
  • the inkjet ink of the present invention is preferably for printing.
  • the ink jet textile printing method of the present invention is an ink jet textile printing method having a step of printing on a fabric by an ink jet method using the ink jet ink of the present invention, and there are the following two embodiments as preferable embodiments.
  • First aspect An ink jet printing method comprising the step of printing directly on a fabric by an ink jet method using the ink jet ink of the present invention.
  • Second aspect A pretreatment step of applying an aqueous pretreatment liquid containing a flocculant to a fabric to obtain a pretreatment fabric, and directly using the inkjet ink of the present invention on a fabric pretreatment with an inkjet method
  • An ink jet printing method comprising the step of printing.
  • “directly printing on a fabric” by the inkjet method does not require a transfer step, and the inkjet ink can be printed directly on the fabric, and a step of applying a printing paste is unnecessary. It refers to both that the inkjet ink is directly printed on the fabric.
  • the ink jet textile printing method of the present invention does not produce waste materials such as waste water and transfer paper, and has an effect of being excellent in the quality (texture) of the colored cloth, the image sharpness and the wet rub fastness with simple workability.
  • the pretreatment step in the second aspect is a step of applying an aqueous pretreatment liquid containing a coagulant to the fabric to obtain a pretreated fabric.
  • the method for applying the aqueous pretreatment liquid to the fabric is not particularly limited, and examples thereof include a coating method, a padding method, an inkjet method, a spray method, a screen printing method, and the like.
  • the aggregating agent contained in the aqueous pretreatment solution is not particularly limited as long as it has an effect of aggregating the dye polymer, and is at least one selected from organic acids, polyvalent metal salts, and cationic compounds. Is preferred.
  • the dye polymer is further fused to the fibers of the fabric by adding the heating step, whereby the fibers are more integrated with the fibers and the texture is not impaired, and the abrasion resistance and the like are further reduced. It has the advantage of being able to be granted.
  • the ink jet printing method of the present invention preferably further includes a heat treatment step.
  • the dye polymer particles can be melted (or softened) by the heat treatment step to improve the adhesion with the fibers (that is, melt dyeing by heat treatment) Can)
  • the colored cloth is preferably subjected to a heat treatment for the purpose of causing the above-mentioned melt dyeing to be performed, and usually it is preferably carried out at 100 to 250 ° C, more preferably 100 to 200 ° C, particularly preferably 120 to It is 200 ° C.
  • the heat treatment time is preferably 30 seconds to 3 minutes.
  • a reactive group for example, a blocked isocyanate group
  • a crosslinking agent for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent
  • the crosslinking reaction is carried out using a reactive group (for example, a blocked isocyanate group) introduced into the polymer, or a crosslinking agent (for example, a blocked isocyanate crosslinking agent or a polyfunctional epoxy crosslinking agent) used in combination as an additive preferable.
  • the heat treatment step is preferably performed at the above temperature
  • the dye polymer is preferably melted at 200 ° C. or less, more preferably 180 ° C. or less. Whether the dye polymer melts at a specific temperature can be confirmed by heating the dye polymer at a temperature of 10 ° C./min to a specific temperature by a melting point meter and visually observing the state of the dye polymer.
  • the cloth (colored cloth) colored by the inkjet textile printing method of the present invention is excellent in the softness and fastness (abrasion resistance) of the texture, but if necessary, the colored cloth may be subjected to a padding treatment over the entire surface. Thus, it is possible to obtain a colored cloth with further improved texture softness and fastness (especially abrasion resistance).
  • Fabrics include synthetic fibers such as nylon, polyester and acrylonitrile, semi-synthetic fibers such as acetate and rayon, natural fibers such as cotton, silk and hair, and mixed fibers thereof, woven fabrics, knitted fabrics, non-woven fabrics, etc. Can be mentioned.
  • a pretreated fabric can also be used as the fabric.
  • the pretreatment liquid can be applied by a coating method, a padding method, an inkjet method, a spray method, a screen printing method or the like.
  • the pretreatment liquid contains an aggregating agent for aggregating the dye polymer, and is preferably an aqueous solution.
  • Examples of the aggregating agent include organic acids, polyvalent metal salts, and cationic compounds.
  • Clothing items include T-shirts, trainers, jerseys, pants, sweat suits, dresses, blouses and the like. It is also suitable for bedding, handkerchiefs, cushion covers, curtains and the like.
  • the present invention also relates to an ink cartridge comprising the inventive inkjet ink, and to an inkjet printer comprising the inventive inkjet ink.
  • the present invention is a colored cloth comprising a fabric and a polymer having a structure derived from a dye and having a crosslinked structure (dye polymer).
  • the fabric and the dye polymer are as described above.
  • the colored cloth of the present invention can be obtained by printing a cloth by the above-mentioned ink jet printing method of the present invention.
  • Q-2 was added to the flask and stirred for 30 minutes after addition, and further stirred at 20 ° C. for 30 minutes. After stirring, 1.8 L of water was added, and the precipitate was collected by filtration to obtain Q-3. 273 g of Q-3, 1.3 L of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and 52 g of tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a three-necked flask and maintained at 110 ° C. .
  • the organic layer was washed with 1450 mL of 0.05 mol / L aqueous hydrochloric acid, and the organic layer was separated and dried over magnesium sulfate, and then the solvent was removed by an evaporator to obtain 350 g of YM-1.
  • Prepolymer 1 is a polyurethane having a structure derived from a dye and a urethane bond, and having an isocyanate group at the end.
  • the prepolymer 2 is a polyurethane containing a carboxyl group and a urethane bond and having an isocyanate group at the end.
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-1) is polyurethane / urea, and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 184 nm.
  • Prepolymer 1-2 is a polyurethane having a structure derived from a dye and a urethane bond, and having an isocyanate group at the end.
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-2) is polyurethane / urea, and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof was 155 nm.
  • Prepolymer 3 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.
  • the obtained emulsion was distilled off under reduced pressure to remove the organic solvent. Thereafter, 1.8 parts by mass of a 10% by mass aqueous solution of UCAT SA102 (manufactured by San-Apro Co., Ltd., trade name) is added to the emulsion, and pure water is added so that the solid content concentration is 15% by mass. Kept for 2 days. Thereafter, coarse particles were removed by filter filtration to obtain 42 parts by mass of a dye polymer water dispersion (ULx-3). The final solid concentration of the dye-polymer water dispersion (ULx-3) was 15% by mass.
  • UCAT SA102 manufactured by San-Apro Co., Ltd., trade name
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-3) is polyurethane / urea and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 105 nm.
  • the prepolymer 4 is a polyurethane containing a carboxyl group and a urethane bond and having an isocyanate group at the end.
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-4) is polyurethane / urea and is a gel having a crosslinked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof Of 109 nm.
  • THF solution of Prepolymer 5 A THF solution of prepolymer 5 was obtained in the same manner as the THF solution of prepolymer 3 except that disperse brown 4 (6.3 parts by mass) was replaced with the following azo dye D-2 (4.7 parts by mass). .
  • the following azo dye D-2 was synthesized according to JP-A-2013-535558.
  • the prepolymer 5 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.
  • a dye polymer water dispersion (ULx-5) was obtained in the same manner as the dye polymer water dispersion (ULx-4) except that the THF solution of the prepolymer 3 was replaced with the THF solution of the prepolymer 5.
  • the final solid concentration of the dye-polymer water dispersion (ULx-5) was 14% by mass.
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-5) is polyurethane / urea and is a gel having a cross-linked structure because it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof was 140 nm.
  • THF solution of Prepolymer 6 A THF solution of prepolymer 6 was obtained in the same manner as the THF solution of prepolymer 3 except that disperse brown 4 (6.3 parts by mass) was replaced with the following phthalocyanine dye D-3 (13.6 parts by mass) .
  • Prepolymer 6 is a polyurethane having a structure derived from a dye and a urethane bond and having an isocyanate group at the end.
  • a dye polymer water dispersion (ULx-6) was obtained in the same manner as the dye polymer water dispersion (ULx-4) except that the THF solution of prepolymer 3 was replaced with the THF solution of prepolymer 6.
  • the final solid content concentration of the dye polymer water dispersion (ULx-6) was 14% by mass.
  • the dye polymer contained in the dye polymer aqueous dispersion (ULx-6) is polyurethane / urea and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP and THF, and the average particle size thereof was 160 nm.
  • the precipitate was reslurried with 400 mL of acetonitrile, collected by filtration, and dried to obtain Q-4.
  • 100 g of Q-4 and 1 L of tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. were placed, dissolved, and maintained at 0 ° C.
  • the final solid concentration of the dye-polymer aqueous dispersion (ALx-1) was 13% by mass.
  • the dye polymer contained in the dye polymer aqueous dispersion (ALx-1) is an acrylic polymer and is a gel having a crosslinked structure since it is insoluble in any solvent of DMSO, NMP, and THF, and the average particle size is It was 140 nm.
  • Example 1 [Preparation of inkjet ink (1)] The following components were mixed at 20 ° C., stirred for 15 minutes, and then filtered through a filter (average pore diameter: 0.8 ⁇ m) to prepare an inkjet ink (1).
  • Dye polymer water dispersion (ULx-1) 3.0 parts by mass Trimethylolpropane 0.060 parts by mass Ultrapure water 0.392 parts by mass 1,2-hexanediol 0.116 parts by mass Glycerin 0.579 parts by mass Triethylene Glycol monobutyl ether 0.119 parts by mass 2-pyrrolidone 0.157 parts by mass Propylene glycol 0.040 parts by mass Surfynol 465 (manufactured by Nisshin Chemical Industry Co., Ltd., trade name) 0.060 parts by mass
  • An ink jet ink (1) is loaded into an ink cartridge, and a polyester fabric (Polyester Tropical (manufactured by Teijin Limited), manufactured by Color Dyeing Company, using an ink jet printer (manufactured by Seiko Epson Corp., Carrario PX-045A, trade name) , Product code A02-01019), cotton fabric (with cotton broadsil, product of dyed products, product code A02-01002), and polyester 65% 35% cotton blend (blended polyester 65 / cotton 35 broad, product of dyed products) The image was printed on product code A02-01030) and dried at 20 ° C. for 12 hours.
  • a polyester fabric Polyter Tropical (manufactured by Teijin Limited), manufactured by Color Dyeing Company
  • an ink jet printer manufactured by Seiko Epson Corp., Carrario PX-045A, trade name
  • Product code A02-01019 Cotton fabric
  • cotton fabric with cotton broadsil, product of dyed products, product code A02-01002
  • heat treatment should be performed at a temperature of 160 ° C and a pressure of 0.20 N / cm 2 for 60 seconds using a heat press (Asahi Textile Co., Ltd., trade name: desktop automatic flat press AF-54 TEN).
  • a heat press Asahi Textile Co., Ltd., trade name: desktop automatic flat press AF-54 TEN.
  • Example 2 An inkjet ink (2) was prepared in the same manner as in Example 1 except that the dye polymer water dispersion (ULx-1) was changed to the dye polymer water dispersion (ULx-2).
  • inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (2) to obtain a colored cloth.
  • Examples 3 to 6 Ink-jet ink (3) to ink-jet ink (3) to Example 1 in the same manner as in Example 1 except that the dye-polymer aqueous dispersion (ULx-1) was changed from dye-polymer aqueous dispersion (ULx-3) to dye-polymer aqueous dispersion (ULx-6) (6) was prepared.
  • inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet inks (3) to (6), to obtain a colored cloth.
  • Example 7 Dye polymer aqueous dispersion (ULx-1) 3.0 parts by mass, dye polymer aqueous dispersion (ULx-4) 1.5 parts by mass, dye polymer aqueous dispersion (ULx-5) 1.5 parts by mass, and An inkjet ink (7) was prepared in the same manner as in Example 1 except that the dye polymer aqueous dispersion (ULx-6) was changed to 0.2 parts by mass.
  • inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (7) to obtain a colored cloth.
  • Example 8 An inkjet ink (8) was prepared in the same manner as in Example 1 except that the dye polymer water dispersion (ULx-1) was changed to the dye polymer water dispersion (ALx-1). In addition, inkjet textile printing was performed in the same manner as in Example 1 except that the inkjet ink (1) was changed to the inkjet ink (8) to obtain a colored cloth.
  • Example 9 [Preparation of aqueous pretreatment liquid A (1) containing flocculant] The following components were mixed and stirred to prepare an aqueous pretreatment liquid A (1).
  • Casio Master PD-7 (Flocculant-containing; made by Yokkaichi Synthetic, solid content 50 mass%) 50g BYK 348 (made by Big Chemie Japan) 5g 100 g of glycerin Water 845g
  • Pretreatment process Polyester fabric (Polyester Tropical (manufactured by Teijin Limited, product name A02-01019) manufactured by Color Dyes Co., Ltd.), cotton fabric (with cotton broadsil, product name A02-01002 manufactured by Color Dyes Co., Ltd.), and polyester
  • the above-prepared aqueous pretreatment solution A (1) is applied to a 65% cotton 35% blend (blended polyester 65 / cotton 35 broad, product name A02-01030, manufactured by Color Dyeing Co., Ltd.) by a padding method, It squeezed by 70% of squeezing rates, and allowed to dry for 24 hours.
  • a squeeze rate (%) represents the remaining amount (mass ratio) of the aqueous treatment liquid to the fabric after squeezing the fabric containing the aqueous treatment liquid.
  • Ink jet printing Inkjet printing was performed in the same manner as in Example 4 except that the above-described pretreated fabric was used as the fabric, to obtain a colored fabric.
  • Example 10 to 12 Inkjet printing was performed in the same manner as in Examples 5 to 7 except that the above-described pretreated fabric was used as the fabric, to obtain a colored fabric.
  • the pigment ink was prepared and filtered through a 0.8 ⁇ m filter to obtain a pigment ink (R2) for comparison.
  • the obtained pigment ink (R2) is loaded into an ink cartridge, and a polyester fabric (polyester tropical (made by Teijin Ltd.), color, using an ink jet printer (manufactured by Seiko Epson Corp., Carrario PX-045A, trade name) Dyeing company, product code A02-01019), cotton fabric (with cotton broadsil, product of dyed product, product code A02-01002), and polyester 65% cotton 35% blend (blend polyester 65 / cotton 35 broad, color dye
  • the image was printed on a product code A02-01030) and dried at 20 ° C. for 12 hours.
  • Example 1 to 12 and Comparative Examples 1 and 2 are shown in Table 1.
  • evaluation of a colored cloth is the result of implementing with the following method.
  • texture and wet rub fastness a cotton fabric was used among the three types of fabrics.
  • the evaluation was made according to the “JIS Handbook 31 Textile” edited by the Japan Standards Association and published in 2015. Image sharpness: Visual sensory evaluation was performed. All three types of fabrics were evaluated in the following four grades: A, two types, B, one type, C, and no image, D.
  • -Texture The untreated cloth before dyeing and the colored cloth after dyeing were touched by hand, and the feeling of the colored cloth was evaluated sensoryally.
  • the inkjet ink of the example of the present invention gives a colored cloth having good image sharpness, texture and wet rub fastness.
  • an ink jet ink capable of providing an image excellent in image sharpness, texture and wet rub fastness, an ink jet printing method using the above ink, and a colored cloth.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

La présente invention concerne : une encre pour jet d'encre contenant une dispersion aqueuse d'un polymère ayant une structure dérivée de colorant et une structure réticulée, un procédé d'impression à jet d'encre comprenant une étape d'impression directe sur un tissu par un système à jet d'encre utilisant l'encre pour jet d'encre ; et un tissu coloré contenant un tissu et un polymère qui a une structure dérivée de colorant et a une structure réticulée.
PCT/JP2018/026223 2017-07-14 2018-07-11 Encre pour jet d'encre, procédé d'impression à jet d'encre et tissu coloré WO2019013265A1 (fr)

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JP2017-138198 2017-07-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022017112A (ja) * 2020-07-13 2022-01-25 富士フイルム株式会社 着色組成物及びその製造方法、カラーフィルタ、並びにキノフタロン色素

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09124989A (ja) * 1995-10-17 1997-05-13 Tektronix Inc インク・ジェット用インク組成物
JP2002509957A (ja) * 1998-03-31 2002-04-02 アベシア・リミテッド 着色ポリウレタン類
JP2002509974A (ja) * 1998-03-31 2002-04-02 アベシア・リミテッド 着色ポリウレタン
JP2004516355A (ja) * 2000-12-20 2004-06-03 アベシア・リミテッド 着色した水消散性ポリウレタン
JP2004161926A (ja) * 2002-11-14 2004-06-10 Canon Inc 重合性化合物、重合体及び着色液
JP2004534142A (ja) * 2001-07-09 2004-11-11 クラリアント・インターナシヨナル・リミテツド 熱可塑性蛍光顔料
JP2004534143A (ja) * 2001-07-13 2004-11-11 ユ セ ベ ソシエテ アノニム エネルギー硬化性重合体インキ組成物
JP2006143883A (ja) * 2004-11-19 2006-06-08 Seiko Epson Corp 着色剤およびそれを用いたインクジェット記録用インク組成物
JP2006176756A (ja) * 2004-10-25 2006-07-06 Hewlett-Packard Development Co Lp 顔料及び染料成分を有する高分子着色剤並びに対応するインク組成物
WO2009157536A1 (fr) * 2008-06-27 2009-12-30 大日精化工業株式会社 Procédé de production d'un polymère colorant, polymère colorant et son utilisation
JP2016069656A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 キサンテン骨格を有する化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、インクジェット記録物、カラーフィルタ、カラートナー、転写用インク、及び捺染用着色組成物
JP2017137468A (ja) * 2016-02-05 2017-08-10 泓瀚科技股▲ふん▼有限公司 水性染料高分子インクジェット印刷用インク組成物

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09124989A (ja) * 1995-10-17 1997-05-13 Tektronix Inc インク・ジェット用インク組成物
JP2002509957A (ja) * 1998-03-31 2002-04-02 アベシア・リミテッド 着色ポリウレタン類
JP2002509974A (ja) * 1998-03-31 2002-04-02 アベシア・リミテッド 着色ポリウレタン
JP2004516355A (ja) * 2000-12-20 2004-06-03 アベシア・リミテッド 着色した水消散性ポリウレタン
JP2004534142A (ja) * 2001-07-09 2004-11-11 クラリアント・インターナシヨナル・リミテツド 熱可塑性蛍光顔料
JP2004534143A (ja) * 2001-07-13 2004-11-11 ユ セ ベ ソシエテ アノニム エネルギー硬化性重合体インキ組成物
JP2004161926A (ja) * 2002-11-14 2004-06-10 Canon Inc 重合性化合物、重合体及び着色液
JP2006176756A (ja) * 2004-10-25 2006-07-06 Hewlett-Packard Development Co Lp 顔料及び染料成分を有する高分子着色剤並びに対応するインク組成物
JP2006143883A (ja) * 2004-11-19 2006-06-08 Seiko Epson Corp 着色剤およびそれを用いたインクジェット記録用インク組成物
WO2009157536A1 (fr) * 2008-06-27 2009-12-30 大日精化工業株式会社 Procédé de production d'un polymère colorant, polymère colorant et son utilisation
JP2016069656A (ja) * 2014-09-30 2016-05-09 富士フイルム株式会社 キサンテン骨格を有する化合物、着色組成物、インクジェット記録用インク、インクジェット記録方法、インクジェットプリンタカートリッジ、インクジェット記録物、カラーフィルタ、カラートナー、転写用インク、及び捺染用着色組成物
JP2017137468A (ja) * 2016-02-05 2017-08-10 泓瀚科技股▲ふん▼有限公司 水性染料高分子インクジェット印刷用インク組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022017112A (ja) * 2020-07-13 2022-01-25 富士フイルム株式会社 着色組成物及びその製造方法、カラーフィルタ、並びにキノフタロン色素
JP7332544B2 (ja) 2020-07-13 2023-08-23 富士フイルム株式会社 着色組成物及びその製造方法、カラーフィルタ、並びにキノフタロン色素

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