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WO2016104248A1 - Agent d'impression textile et produit en tissu - Google Patents

Agent d'impression textile et produit en tissu Download PDF

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Publication number
WO2016104248A1
WO2016104248A1 PCT/JP2015/085051 JP2015085051W WO2016104248A1 WO 2016104248 A1 WO2016104248 A1 WO 2016104248A1 JP 2015085051 W JP2015085051 W JP 2015085051W WO 2016104248 A1 WO2016104248 A1 WO 2016104248A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
pigment
urethane resin
polycarbonate
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/085051
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English (en)
Japanese (ja)
Inventor
智子 木戸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2016525112A priority Critical patent/JP6119919B2/ja
Publication of WO2016104248A1 publication Critical patent/WO2016104248A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • 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
    • D06P1/52—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 using compositions containing synthetic macromolecular substances
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06Q—DECORATING TEXTILES
    • D06Q1/00—Decorating textiles

Definitions

  • the present invention relates to a printing agent and a fabric using the same.
  • a pigment printing method using a water-based pigment printing agent is known as a printing method for printing images such as letters, pictures and designs on fabrics such as woven fabrics, nonwoven fabrics and knitted fabrics.
  • the pigment printing method is a method in which a pigment printing agent containing a color pigment and a binder resin is printed, and then fixed to a substrate through a drying and curing step as necessary.
  • this printing method include a silk screen method (for example, see Patent Document 1) in which a pattern of a screen bag is continuously printed on a cloth, an ink jet recording method in which ink is ejected from a nozzle and adhered to the cloth (for example, see Patent Document 2). )It has been known.
  • pigment printing methods do not require the selection of colorants depending on the fiber type, the processing method is simple, and there is no need for steaming, water washing or soaping processes, so there is no energy cost. . Moreover, since no waste liquid is generated, it is a safe processing method in terms of environment.
  • the pigment printing method is different from the printing method using a dye, and the pigment as the color material is physically fixed to the fabric with a binder resin, so that the printing portion is removed from the fabric by washing or external friction. There were problems such as peeling (fastness to washing) and poor texture.
  • the binder resin is easily formed into a film, sometimes the binder resin is dried and fixed, and a water-insoluble resin film is stretched to cause a problem such as clogging of the screen flaw.
  • the highlight portion is likely to be clogged because it dries quickly.
  • the printing operation is stopped with the pigment printing agent remaining on the plate, the pigment printing agent is dried on the plate, and when the printing operation is resumed, the dried and fixed pigment printing agent is easily dissolved again. (This is hereinafter referred to as re-dissolvability) is difficult to transfer, and printing is not possible.
  • the storage stability of the pigment printing agent may decrease due to the compatibility with various solvents blended in the pigment printing agent. There is also a problem that it is difficult to obtain vivid colors such as dyes. As described above, since the pigment printing agent is greatly affected by the binder resin to be blended, a binder resin suitable for the pigment printing agent has been developed.
  • Urethane resins have been studied as binder resins suitable for pigment printing agents.
  • textile printing inks for inkjet recording using a polyurethane resin using a polyether polyol as a binder resin are resistant to abrasion and dry. It describes that it is excellent in cleaning property and ejection stability.
  • Patent Document 5 describes that a pigment printing binder made of an aqueous dispersion of a polyurethane resin using a polycarbonate diol has a low heat blocking property and a good dry cleaning resistance.
  • Patent Document 6 describes that a white pigment ink jet recording printing ink using a urethane resin having a specific range of film elongation, tensile strength, and zeta potential is excellent in white ink color development and washing fastness. Has been.
  • Patent Documents 3 to 6 describe knowledge about abrasion resistance, fastness to washing, and dry cleaning resistance.
  • Patent Documents 3 to 6 describe knowledge about abrasion resistance, fastness to washing, and dry cleaning resistance.
  • the present invention is to provide a printing agent which is excellent in storage stability, has good color developability when a colored pigment is used, and has an excellent texture.
  • the present inventors can use the silk screen method or the inkjet recording method without any problem, storage stability, re-dissolvability. It has been found that a printing agent excellent in washing fastness, good texture and excellent color development (printing density) can be obtained.
  • the present invention provides a printing agent comprising a pigment, water, an organic solvent, and a binder resin, wherein the binder resin is a polycarbonate urethane resin having a breaking elongation of 300% or more. To do.
  • the present invention also provides a fabric product obtained by printing the above-described printing agent on a fabric.
  • the printing agent of the present invention is excellent in storage stability by using a polycarbonate-based urethane resin having specific physical properties as a binder resin, and the fabric obtained by printing the printing agent on the fabric has good color development and texture. Excellent. Further, the printing agent of the present invention can be used without any problem whether it is a silk screen method or an ink jet recording method.
  • the pigment used in the present invention is not particularly limited, and any pigment that is usually used in pigment printing agents can be used without particular limitation.
  • known inorganic pigments and organic pigments that can be dispersed in water or water-soluble organic solvents can be used.
  • the inorganic pigment include carbon black produced by a known method such as titanium oxide, iron oxide, a contact method, a furnace method, and a thermal method.
  • Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelates, acidic dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like.
  • azo pigments including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments
  • polycyclic pigments for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines.
  • pigments include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Moul 660R, Regul 660R, Regul 660R 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc.
  • pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.
  • pigments used in magenta ink include C.I. I.
  • Pigment violet 19 C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, and these Examples thereof include a mixture or a solid solution of at least two kinds of pigments selected from pigments.
  • pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 63, 66, and the like.
  • Specific examples of the pigment used in the red ink include C.I. I.
  • Pigment Red 17, 49: 2, 112, 149, 150, 177, 178, 179, 188, 254, 255, and 264 are preferably used.
  • pigments used in orange ink include C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, 71, 73, 81, and the like.
  • pigments used in green ink include C.I. I. Pigment green 7, 10, 36, 58, 59, and the like.
  • pigments used in violet ink include C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.
  • a so-called self-dispersing pigment surface-treated pigment having a water dispersibility-imparting group on the pigment surface and capable of stably maintaining the dispersion state without a dispersant
  • So-called capsule pigments water-dispersible polymer-containing pigments that can be stably maintained without a dispersant, or pigments dispersed with a dispersant may be used.
  • the pigment used in the present invention can be either dry powder or wet cake. Moreover, these pigments may be used independently and may be used in combination of 2 or more types.
  • the pigment used in the present invention is preferably a pigment having a particle size of 25 ⁇ m or less, and particularly preferably a pigment having a particle size of 1 ⁇ m or less.
  • a value measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) can be adopted.
  • water As the water used in the present invention, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used.
  • pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water
  • the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold or bacteria can be prevented when the ink composition is stored for a long period of time.
  • the water functions as a medium for pigments and binder resins as a printing agent.
  • the medium is mostly water, and a partly water-soluble solvent is often added.
  • the ratio of water: water-soluble solvent is generally used in the range of 4: 1 to 1: 1.
  • Organic solvent As the organic solvent used in the present invention, any of those conventionally used in screen recording inks for printing and water-based inkjet recording inks can be used. Organic solvents are broadly classified into those that function as humectants and those that function as penetrating solvents.
  • the humectant include, for example, glycerin, ethylene glycol adducts of glycerin (specific examples: liponic EG-1 (manufactured by Lipochemical)), diglycerin, polyglycerin, ethylene glycol, propylene glycol, 1, 3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol (specific examples: “# 200”, “# 300”, “# 400”, “# 4000”, “# 6000” manufactured by Wako Pure Chemical Industries, Ltd.), 2- Examples include pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, thiodiglycol, sulfolane, dimethyl sulfoxide, neopentyl alcohol, trimethylolpropane, and 2,2-dimethylpropanol. These organic solvents can be used alone or in combination of two or more.
  • penetrating solvent examples include monohydric or polyhydric alcohols, amides, ketones, ketoalcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, polyalkylene glycols, propylene.
  • Glycol dipropylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-hexanediol 1,6-hexanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2,6-hexanetriol, Polyols such as trimethylolpropane and pentaerythritol, diethylene glycol Polyhydric alcohol alkyl ethers such as monobutyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol mono
  • organic solvents can be used alone or in combination of two or more. From the viewpoint of resolubility, at least one selected from 1,2-propanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, triethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether should be selected. It is preferable to use 3-methyl-1,5-pentanediol.
  • the content of the penetrant in the printing agent is preferably 3 to 15% by mass with respect to the total amount of the printing agent. If it is less than 3% by mass, the re-solubility may be lowered, and if it exceeds 15% by mass, the water resistance of the printed part may be insufficient, which may affect washing fastness. .
  • Binder resin a polycarbonate urethane resin having a breaking elongation of 300% or more is used as the binder resin.
  • the polycarbonate-based urethane resin means a urethane resin having a carbonate bond, and specifically means a urethane resin having a polycarbonate structure of the general formula (1).
  • R represents an arbitrary group
  • n represents the number of repetitions.
  • the elongation at break of the polycarbonate urethane resin is preferably 300% to 1000%, more preferably 410% to 800%, and most preferably 410% to 600%.
  • the breaking elongation was measured as follows. Universal tensile testing machine (Shimadzu Corporation) sampled into a rectangular shape with a length of 50 mm in the direction perpendicular to the main shrinkage direction (film width direction) and a length of 5 mm in the main shrinkage direction (film longitudinal direction). Manufactured by Autograph (registered trademark)), both ends of the test piece (both ends in the longitudinal direction) are gripped, a tensile test is performed at a tensile speed of 300 mm / min, and the elongation at break is defined as the elongation at break. did.
  • the polycarbonate urethane resin used in the present invention can be used without particular limitation as long as it is a polycarbonate urethane resin having a breaking elongation of 300% or more.
  • a polycarbonate-based urethane resin having a hydrophilic group is preferable from the viewpoint of ease of dispersibility in water, which is a solvent for printing agents.
  • a polycarbonate polyol (a1-1) and a polyol (a1-2) having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group a polycarbonate-type urethane resin (A) which has the structural unit derived from the polyol (a1) to contain and the structural unit derived from polyisocyanate (a2) is mentioned.
  • the polycarbonate polyol (a1-1) and an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene group are used. It is preferable to use a polyol (a1-2) having a hydrophilic group which is a polyoxypropylene group.
  • Polycarbonate polyol (a1-1) As the polycarbonate polyol (a1-1), for example, a polycarbonate polyol (a1-1) having a structural unit derived from a carbonate ester and a structural unit derived from a polyol is preferable. This can be obtained, for example, by reacting a carbonate ester with a polyol, preferably an aliphatic diol, as raw materials.
  • carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
  • low molecular weight polyol examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc.
  • Aliphatic diols such as Sphenol-A, bisphenol-F, 4,4'-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate Polyester polyols such as polycaprolactone can be used. Among them, a relatively low molecular weight aliphatic chain diol is preferably used.
  • Preferred aliphatic chain diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like.
  • the number average molecular weight is preferably 50 to 250.
  • the polycarbonate polyol (a1-1) is preferably used in an amount of 80 to 99% by mass, more preferably based on the total mass of the polyol (a1) used for the production of the polycarbonate-based urethane resin (A). 85 to 99% by mass.
  • the polycarbonate polyol (a1-1) is used in a range of 10 to 90% by mass with respect to the total mass of the polyol (a1) and polyisocyanate (a2) used in the production of the polycarbonate-based urethane resin (A). It is preferable to do.
  • the polycarbonate-based urethane resin (A) used in the present invention preferably has an anionic group, a cationic group, or a nonionic group for imparting dispersion stability in a printing agent, and among them, an anionic group or a cationic group. It preferably has a functional group.
  • polyol (a1-2) having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group may be simply referred to as “polyol (a1-2)”. is there.
  • Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group.
  • a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like is preferable for maintaining good water dispersibility.
  • Examples of basic compounds that can be used when neutralizing part or all of the carboxyl group and sulfonic acid group as the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, An alkanolamine such as ethanolamine, a metal base compound containing Na, K, Li, Ca, or the like can be used. Among them, it is preferable to select an organic amine having a boiling point of 100 ° C. or less from the viewpoint of reducing the residue on the dry film.
  • examples of the cationic group include a tertiary amino group.
  • examples of the acid that can be used when neutralizing part or all of the tertiary amino group include formic acid and acetic acid.
  • a quaternizing agent that can be used when quaternizing a part or all of the tertiary amino group, for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.
  • nonionic group examples include polyoxyalkylene groups such as polyoxyethylene group, polyoxypropylene group, polyoxybutylene group, poly (oxyethylene-oxypropylene) group, and polyoxyethylene-polyoxypropylene group. Is mentioned. Of these, a polyoxyalkylene group having an oxyethylene unit is preferable for further improving the hydrophilicity.
  • polyol (a1-2) for example, an anionic group-containing polyol, a cationic group-containing polyol, and a nonionic group-containing polyol other than the polycarbonate polyol (a1-1) described above can be used. Especially, it is preferable to use an anionic group containing polyol or a cationic group containing polyol, and it is more preferable to use an anionic group containing polyol.
  • anionic group-containing polyol examples include a carboxyl group-containing polyol and a sulfonic acid group-containing polyol.
  • carboxyl group-containing polyol examples include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and dicarboxylic acids thereof.
  • examples thereof include a carboxyl group-containing polyester polyol obtained by reacting with an acid. Of these, 2,2′-dimethylolpropionic acid is preferred.
  • Examples of the cationic group-containing polyol include a tertiary amino group-containing polyol. Specifically, the reaction of N-methyl-diethanolamine or a compound having two epoxies in one molecule with a secondary amine. The polyol which is a thing is mentioned.
  • nonionic group-containing polyol examples include polyalkylene glycol having a structural unit derived from ethylene oxide.
  • the polyol (a1-2) is preferably used in the range of 0.3% by mass to 15.0% by mass with respect to the total amount of the polyol (a1) used in the production of the polycarbonate-based urethane resin (A). .
  • the hydrophilic group When the hydrophilic group is present in an amount of 100 mmol / kg to 1200 mmol / kg with respect to the whole of the polycarbonate-based urethane resin (A), it imparts better water dispersibility, and in the range of 150 mmol / kg to 1000 mmol / kg. More preferably.
  • the acid value is preferably in the range of 15 to 50 mgKOH / g, and more preferably in the range of 20 to 45 mgKOH / g.
  • the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said polycarbonate-type urethane resin (A).
  • polyol (a1) in addition to the polycarbonate polyol (a1-1) and the polyol (a1-2), other polyols can be used in combination as long as the effects of the present invention are not impaired.
  • other polyol for example, a polyol used as a raw material for the polycarbonate polyol (a1-1) can be used.
  • Polyisocyanate (a2) examples of the polyisocyanate (a2) that can react with the polyol (a1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, Contains aromatic polyisocyanates such as naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, etc. Use polyisocyanate It can be.
  • polyisocyanate (a2) it is preferable to use an aliphatic polyisocyanate such as hexamethylene diisocyanate or an aliphatic cyclic structure-containing polyisocyanate such as isophorone diisocyanate from the viewpoint of suppressing yellowing of the printed part.
  • an aliphatic polyisocyanate such as hexamethylene diisocyanate or an aliphatic cyclic structure-containing polyisocyanate such as isophorone diisocyanate from the viewpoint of suppressing yellowing of the printed part.
  • the polyisocyanate (a2) is composed of the polyol (a1) and the polyisocyanate (a2) used in the production of the polycarbonate urethane resin (A) because the polycarbonate urethane resin (A) has a breaking elongation of 300% or more. It is preferable to use in the range of 12 to 30% by mass with respect to the total mass.
  • the polycarbonate-based urethane resin (A) has a polycarbonate polyol (a1-1) and a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as described above.
  • polyamine other active hydrogen atom-containing compounds and the like can be used.
  • the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine, dihydrazisuccinate
  • the chain extender is preferably 3 parts by mass or less with respect to the total mass of the polyol (a1), polyisocyanate (a2) and chain extender used in the production of the polycarbonate-based urethane resin (A). More preferably, it is used in the range of 5% by mass or less, and more preferably in the range of 0.5% by mass or less.
  • the printing agent of this invention may use the crosslinking agent (F) mentioned later for the purpose of improving wash fastness and friction fastness further.
  • the polycarbonate urethane resin (A) may be one having a functional group [X] capable of crosslinking reaction with the functional group of the crosslinking agent (F). preferable.
  • the functional group [X] include a carboxyl group and a carboxylate group that can be used as the hydrophilic group.
  • the carboxyl group or the like contributes to the water dispersion stability of the polycarbonate-based urethane resin (A) in an aqueous medium, and when they undergo a crosslinking reaction, they also act as the functional group [X], and the crosslinking agent ( F) can be partially crosslinked.
  • the polycarbonate-based urethane resin (A) preferably has an acid value of 2 to 55, and has an acid value of 15 to 50 It is preferable to improve the fastness to washing and friction fastness.
  • the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said polycarbonate-type urethane resin (A).
  • an active hydrogen-containing compound that can react with the polyisocyanate (a2) may be reacted within a range that does not impair the effects of the present invention.
  • the weight-average molecular weight of the polycarbonate-based urethane resin (A) is preferably 5000 to 200000, more preferably 20000 to 100000 from the viewpoints of wash fastness, friction fastness, texture, and re-solubility. More preferably, it is 30000-70000.
  • the polycarbonate-based urethane resin (A) is produced, for example, by reacting the polyol (a1) with the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent. Then, when there is a hydrophilic group in the polycarbonate-based urethane resin (A), a neutralized part or all of the hydrophilic group as necessary is mixed in an aqueous medium to make it aqueous. Can be manufactured.
  • the polycarbonate-type urethane resin (A) by which chain extension was carried out can be manufactured by mixing with an aqueous medium in the case of the said aqueous
  • the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5.
  • it is carried out in the range of 0.9 to 1.5.
  • Examples of the organic solvent that can be used in producing the polycarbonate urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; and acetates such as ethyl acetate and butyl acetate.
  • ketones such as acetone and methyl ethyl ketone
  • ethers such as tetrahydrofuran and dioxane
  • acetates such as ethyl acetate and butyl acetate.
  • Nitriles such as acetonitrile
  • amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.
  • the polycarbonate-based urethane resin (A) produced by the above method is made hydrophilic, for example, by hydrophilicity of the aqueous polycarbonate-based urethane resin (A) obtained by reacting the polyol (a1) with the polyisocyanate (a2). After neutralizing or quaternizing part or all of the sex group, water can be added and dispersed in water. In that case, you may use an emulsifier as needed. In addition, when dissolving or dispersing water, a machine such as a homogenizer may be used as necessary.
  • emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • Anionic emulsifiers; cationic amines such as alkylamine salts, alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts It is below.
  • Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof.
  • Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; lactams such as N-methyl-2-pyrrolidone, and the like.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
  • the polycarbonate urethane resin (A) thus obtained is in a state where the polycarbonate urethane resin (A) is dispersed in an aqueous medium.
  • the polycarbonate-based urethane resin (A) is in the form of an aqueous dispersion dispersed in an aqueous medium.
  • the aqueous medium is contained in the range of 20% by mass to 90% by mass with respect to the total amount of the composition of the polycarbonate-based urethane resin (A). Is preferable in obtaining.
  • the particle size of the aqueous dispersion of the polycarbonate urethane resin (A) is preferably in the range of 3 nm to 1000 nm, more preferably 5 nm to 400 nm.
  • the particle size means “average particle size D50” of an aqueous dispersion of polycarbonate urethane resin (A) diluted to a solid content of 5%, and a particle size distribution meter (“Microtrack UPA150” manufactured by Nikkiso Co., Ltd.).
  • the average value of D50 (indicating that 50% of the particles are smaller than or equal to this particle size) in the particle size distribution measured three times in (3) is defined as the average particle size D50.
  • the ratio of the polycarbonate urethane resin to the pigment may be a ratio in a range usually used for screen recording ink or ink jet recording ink.
  • the ratio of the urethane resin to the pigment is in the range of 1: 3 to 8: 1. preferable.
  • the fastness to washing and the fastness to friction contribute to the molecular weight of the urethane resin used, and the higher the molecular weight of the urethane resin, the better the fastness to washing and the fastness to friction.
  • excessive use of a high molecular weight urethane resin in the ink leads to higher viscosity, so it is preferable to determine the amount used in consideration of the balance with viscosity.
  • the urethane resin used in the present invention is a binder resin for fixing the pigment on the fiber.
  • the ratio of the binder resin to the pigment in the printing agent is generally used in the range of 1: 3 to 8: 1, preferably 1: 1 to 8: 1, preferably 1: 1 to 5: 1. Most preferred.
  • the textile printing agent of the present invention can be prepared by preparing a high-concentration aqueous dispersion (pigment paste) of the pigment, diluting it with water, and adding the binder resin and other additives as required. it can.
  • the method for obtaining the pigment paste by dispersing the pigment in the water is not particularly limited, and it is preferable to use a known dispersion method.
  • the dispersant used at this time may be dispersed in water using a known pigment dispersant, or a surfactant may be used.
  • the pigment dispersant is preferably an aqueous resin, and preferable examples include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, styrene-methacrylic acid. Styrenes such as acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene- ⁇ -methylstyrene-acrylic acid copolymers, styrene- ⁇ -methylstyrene-acrylic acid-acrylic acid ester copolymers, etc.
  • Examples thereof include acrylic resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.
  • the compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine.
  • the amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
  • Commercially available products include Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, EFKA series manufactured by Ciba Specialty Chemicals.
  • Examples of the dispersion method include the following (1) to (3).
  • (2) The pigment and the pigment dispersant are kneaded using a kneader such as two rolls or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is then mixed using a stirring / dispersing device.
  • a method of preparing a paste A method of preparing a paste.
  • the kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, and a planetary mixer.
  • the stirring / dispersing device is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, an SC mill, and a nanomizer.
  • an ultrasonic homogenizer a high-pressure homogenizer
  • a paint shaker a paint shaker
  • a ball mill a roll mill
  • a sand mill a sand grinder
  • a dyno mill a disperse mat
  • SC mill and a nanomizer.
  • One of these may be used alone, or two or more devices may be used in combination.
  • the amount of pigment in the pigment paste is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.
  • the pigment amount is less than 5% by mass, the water-based ink prepared from the pigment paste is insufficiently colored, and a sufficient image density tends not to be obtained.
  • the amount is more than 60% by mass, the dispersion stability of the pigment tends to decrease in the pigment paste.
  • an impurity removal step by ion exchange treatment or ultrafiltration treatment may be performed, followed by post-treatment.
  • Ion exchange treatment can remove ionic substances such as cations and anions (divalent metal ions, etc.), and by ultra-treatment, impurities dissolved substances (residual substances during pigment synthesis, excess components in dispersion composition) , Resin not adsorbed to the organic pigment, mixed foreign matter, etc.) can be removed.
  • a known ion exchange resin is used in the ion exchange treatment.
  • the ultratreatment uses a known ultrafiltration membrane and may be either a normal type or a double capacity up type.
  • the pigment paste is prepared, it is appropriately diluted and an additive as necessary is added to obtain a printing agent suitable for a preferred processing method such as dip dyeing or printing according to the fiber to be colored.
  • printing agents for screen recording use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. as final additives, and final pigments
  • concentration is preferably in the range of 1 to 10% by mass.
  • the additive is preferably added together with the binder resin.
  • printing agents for dyeing use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, and binder resins as additives
  • the final pigment concentration is preferably in the range of 1 to 10% by mass.
  • the viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa ⁇ s to 100 mPa ⁇ s.
  • the use of a printing agent for spray printing uses a binder resin as a viscosity modifier, a pH adjuster, a chelating agent, a plasticizer, an antioxidant, an ultraviolet absorber, etc. as an additive.
  • the pigment concentration is preferably in the range of 1 to 10% by mass.
  • the viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa ⁇ s to 100 mPa ⁇ s.
  • printing agents for ink jet recording use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. as additives.
  • the pigment concentration is preferably 1 to 20% by mass in order to obtain a sufficient image density and to ensure the dispersion stability of the pigment in the ink.
  • the additive is preferably added together with the binder resin.
  • preservatives or fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3- ON (Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, Proxel DL from Arch Chemicals) and the like.
  • the viscosity modifier include mainly water-soluble natural or synthetic polymers such as carboxymethyl cellulose, sodium polyacrylate, polyvinyl pyrrolidone, gum arabic, and starch.
  • pH adjuster examples include collidine, imidazole, phosphoric acid, 3- (N-morpholino) propanesulfonic acid, tris (hydroxymethyl) aminomethane, boric acid and the like.
  • chelating agents include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramildiacetic acid, Examples include 1,2-diaminocyclohexane-N, N, N ′, N′-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid, and salts thereof (including hydrates).
  • antioxidant or ultraviolet absorber examples include allophanates such as allophanate and methyl allophanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, L-ascorbic acid and its salts, etc. manufactured by Ciba Geigy Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, or the like, or a lanthanide oxide or the like.
  • allophanates such as allophanate and methyl allophanate
  • biurets such as biuret, dimethylbiuret and tetramethylbiuret
  • L-ascorbic acid and its salts etc. manufactured by Ciba Geigy Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irg
  • the method for adding the diluent and additives can be performed by any conventional method without particular limitation.
  • the pigment paste is mixed with a binder resin, a surfactant, a viscosity modifier, an antifoaming agent, an antioxidant or an ultraviolet absorber, an antiseptic, and the like as additives.
  • a machine or a stirrer such as a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, an ultrahigh pressure homogenizer, or a pearl mill. If necessary, various additives may be further added thereafter.
  • a water-soluble organic solvent may be further added for the purpose of stably dissolving or dispersing the additive, the pigment, the pigment dispersant, and the urethane resin.
  • water-soluble solvent examples include mono- or polyhydric alcohols, amides, ketones, ketoalcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, polyalkylene glycols, and glycerin.
  • saccharides can be used for the same purpose. Examples include monosaccharides and polysaccharides, in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. Alginic acid and its salts, cyclodextrins, and celluloses can be used.
  • the printing agent of the present invention may contain a surfactant in order to control its permeability.
  • the surfactant used in this case is preferably one having good compatibility with other components present in the printing agent of the present invention. Further, a surfactant having high penetrability and stability is preferable.
  • amphoteric surfactants and nonionic surfactants.
  • amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and others Examples include imidazoline derivatives.
  • nonionic surfactants include acetylene glycol surfactants, acetylene alcohol surfactants, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl.
  • Ethers such as allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester , Sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxy Examples include esters such as tylene monooleate and polyoxyethylene stearate, silicon surfactants such as dimethylpolysiloxane, fluorine-containing surfactants such as other fluorine alkyl esters and perfluoroalkyl carboxylates, and the like.
  • acetylene glycol surfactants and acetylene alcohol surfactants are preferred. When these surfactants are added to the ink composition, they are preferable because they have less foaming properties and have an excellent antifoaming function.
  • Specific examples of acetylene glycol surfactants and acetylene alcohol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne- 3,6-diol, 3,5-dimethyl-1-hexyne-3ol and the like are available, and are commercially available.
  • Surfynol 61, 82, 104, 465 manufactured by Air Products (UK) 485, TG, Olphine STG from Nissin Chemical Industry Co., Ltd., Olfin E1010, and the like.
  • the addition amount of the surfactant is preferably 0.01 wt% or more and 10 wt% or less with respect to the total amount of the printing agent, and a more preferable upper limit value is 5.0 wt%, and a preferable lower limit value is 0.5% by weight.
  • the surface tension is preferably adjusted to 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, More preferably, it is 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, when it exceeds 60 mN / m, there is a tendency that the non-absorbing base material is easily repelled.
  • the viscosity is preferably 1.2 mPa ⁇ s or more and 20.0 mPa ⁇ s or less, more preferably 2.0 mPa ⁇ s or more and less than 15.0 mPa ⁇ s, and further preferably 3.0 mPa ⁇ s or more and 12. Less than 0.0 ⁇ mPa ⁇ s.
  • the surface tension can be appropriately adjusted by the surfactant.
  • a crosslinking agent having two or more groups having reactivity with the crosslinkable functional groups of the dispersion resin and the binder resin may be added.
  • cross-linking agents amino resins such as melamine resin, benzoguanamine resin, urea resin, phenol resin such as trimethylolphenol and its condensate, tetramethylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, xylylene diisocyanate
  • Polyisocyanates such as modified isocyanates and blocked isocyanates, aliphatic amines, aromatic amines, N-methylpiperazine, amines such as triethanolamine, morpholine, dialkylaminoethanol, benzyldimethylamine, polycarboxylic acids, anhydrous Phthalic acid, maleic anhydride, hexahydrophthalic an
  • the addition amount to the printing agent of the present invention it is necessary to add an amount commensurate with the number of crosslinkable functional groups of the dispersing resin and binder resin to be reacted, preferably 20% by mass or less, more preferably 10% by mass or less. More preferably, it is 5% by mass or less.
  • an amount commensurate with the number of crosslinkable functional groups of the dispersing resin and binder resin to be reacted preferably 20% by mass or less, more preferably 10% by mass or less. More preferably, it is 5% by mass or less.
  • the printing agent of the present invention can print on fabric, artificial leather, natural leather and the like. Particularly excellent for printing on fabrics. It is also possible to print on general-purpose adherends such as paper.
  • the fabric used in the present invention is preferably a medium composed of fibers, and may be a non-woven fabric or a non-woven fabric. As the material, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, or rayon can be used.
  • Measuring device High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000” (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection amount: 100 ⁇ L (THF solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was prepared using the following standard polystyrene.
  • ⁇ Measurement method of elongation at break Universal tensile testing machine (Shimadzu Corporation) sampled into a rectangular shape with a length of 50 mm in the direction perpendicular to the main shrinkage direction (film width direction) and a length of 5 mm in the main shrinkage direction (film longitudinal direction). Manufactured by Autograph (registered trademark)), grasping both ends (both ends in the longitudinal direction) of the test piece, conducting a tensile test under the condition of a tensile speed of 300 mm / min, and determining the elongation at break as the elongation at break did.
  • the acid value was calculated based on the use amount of an acid group-containing compound such as a carboxyl group-containing polyol used for the synthesis of the urethane resin.
  • polyurethane “PUD-1” having a weight average molecular weight of 46000 (acid value) 25) of an organic solvent solution was obtained. Thereafter, it is cooled to 50 ° C., 31.3 parts by mass of triethylamine and 2169 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • a resin composition having a nonvolatile content of 23% by mass (breaking elongation: 480%) in which the urethane resin was dispersed in an aqueous medium was obtained.
  • polyurethane “PUD-2” (acid) having a weight average molecular weight of 34,000 was obtained. Of 20) was obtained. Thereafter, it is cooled to 50 ° C., 29.7 parts by mass of triethylamine and 2057 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 500%) in which the urethane resin was dispersed in an aqueous medium was obtained.
  • polyurethane “PUD-3” (acid) with a weight average molecular weight of 37000 was added.
  • An organic solvent solution having a value of 25) was obtained. Thereafter, the mixture is cooled to 50 ° C., 29.8 parts by mass of triethylamine and 2069 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • a resin composition having a nonvolatile content of 23% by mass (breaking elongation: 320%) in which the urethane resin was dispersed in an aqueous medium was obtained.
  • polyurethane “PUD-4” (acid 15) of an organic solvent was obtained. Thereafter, it is cooled to 50 ° C., 16.8 parts by mass of triethylamine and 1957 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • polyurethane “PUD-6” having a weight average molecular weight of 54,000 (acid value) 30) of an organic solvent solution was obtained. Thereafter, it is cooled to 50 ° C., 39.0 parts by mass of triethylamine and 2588 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • a resin composition having a nonvolatile content of 23% by mass (breaking elongation: 530%) in which the urethane resin was dispersed in an aqueous medium was obtained.
  • polyurethane “PUD-7” having a weight average molecular weight of 51000 (acid value) 35) of an organic solvent solution was obtained. Thereafter, the mixture is cooled to 50 ° C., 47.4 parts by mass of triethylamine and 2689 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • polyurethane “PUD-8” having a weight average molecular weight of 50000 (acid value) 40) of an organic solvent solution was obtained. Thereafter, it is cooled to 50 ° C., 56.4 parts by mass of triethylamine and 2795 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration.
  • a resin composition having a nonvolatile content of 23% by mass (breaking elongation of 460%) in which the urethane resin was dispersed in an aqueous medium was obtained.
  • 1504 parts by mass of water was added.
  • 17.3 parts by mass of ethylenediamine was added and reacted.
  • methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C.
  • 1502 parts by mass of water was added.
  • 15.3 parts by mass of ethylenediamine was added and reacted.
  • methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C.
  • a pigment paste was obtained in the same manner as the pigment paste (A), except that the copper phthalocyanine pigment of the pigment paste (A) was changed to a quinacridone pigment (product name Fastogen Super Magenta RG manufactured by DIC).
  • a pigment paste was obtained in the same manner as the pigment paste (A), except that the copper phthalocyanine pigment of the pigment paste (A) was changed to a disazo pigment (product name Novoperperm Yellow 4G01 manufactured by Clariant).
  • a pigment paste was obtained in the same manner as the pigment paste (A) except that the copper phthalocyanine pigment of the pigment paste (A) was changed to carbon black (product name # 40 manufactured by Mitsubishi Chemical Corporation).
  • ⁇ Preparation of printing agent 20 parts of the pigment paste (A), a solvent (water, water-soluble solvent, oil-soluble solvent, etc.), and 4 parts of PUD-1 (in terms of solid content) as a urethane resin were added to obtain a printing agent of the example. .
  • the composition of each printing agent is shown in the attached table. At the time of addition in each example, the mixture was sufficiently stirred with a dispersion stirrer (TK Homo Disper L manufactured by Tokushu Kika Kogyo Co., Ltd.).
  • Printing evaluation was performed by a screen printing method using an auto screen printing machine (manufactured by Sakurai Dyeing Machine Co., Ltd.). Each ink was printed on a polyester / cotton fabric on a 135 mesh striped screen, dried at 120 ° C. for 2 minutes, and then subjected to heat treatment at 150 ° C. for 2 minutes. As a result of visual inspection of the printed material, all the products were of good quality.
  • ⁇ Dry and wet friction fastness evaluation method A printed material obtained by screen printing is subjected to a dry type and a wet type test using a Gakushin type friction fastness tester according to JIS L 0849: 2004, and then a change of JIS L 0801: 2004 Grades were graded from 1st to 5th grades according to the visual criteria using the gray scale for fading. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.
  • ⁇ Texture evaluation method> The evaluation fabric obtained above was evaluated by the tentacles according to the following criteria. ⁇ : The touch between the printed surface and the fabric is not felt or is slightly felt. (Triangle
  • a texture evaluation method in accordance with JIS L 1913: 2010, using a bending resistance tester (cantilever method, Gurley method, handle ohm method, etc.) Evaluation is preferred. The texture becomes softer as the bending resistance is smaller, and the texture becomes harder as it is larger.
  • Tables 4 to 6 show the compositions and various evaluation results of the printing agents of Examples and Comparative Examples.
  • the unit of blending in the table is part.
  • PC polycarbonate polyol PE: polyoxytetramethylene glycol DMPA: 2,2-dimethylolpropionic acid
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • BTG triethylene glycol monobutyl ether
  • MPD 3-methyl 1,5 -Pentanediol
  • NCO content %): mass% of polyisocyanate with respect to the total mass of all polyols and polyisocyanate used in the production of polycarbonate-based urethane resin
  • NH content Mass% of chain extender with respect to the total mass of all polyols, polyisocyanate and chain extender

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Coloring (AREA)

Abstract

L'invention concerne un agent d'impression textile qui contient un pigment, de l'eau, un solvant organique et une résine liante, et qui est caractérisé en ce que la résine liante est une résine polycarbonate uréthane qui présente un allongement à la rupture supérieur ou égal à 300 %, ainsi qu'un produit en tissu qui est obtenu par impression de l'agent d'impression textile sur un tissu. Il est préférable que la résine polycarbonate uréthane présente un motif constituant dérivé d'un polyisocyanate aliphatique ou d'un polyisocyanate contenant une structure alicyclique. Il est également préférable que la résine polycarbonate uréthane présente un indice d'acide dans la plage de 15 à 50 mg de KOH/g et un poids moléculaire moyen en poids dans la plage de 5 000 à 200 000.
PCT/JP2015/085051 2014-12-24 2015-12-15 Agent d'impression textile et produit en tissu Ceased WO2016104248A1 (fr)

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JP2018053170A (ja) * 2016-09-30 2018-04-05 セイコーエプソン株式会社 捺染インクジェットインク組成物及び記録方法
JP2018123235A (ja) * 2017-01-31 2018-08-09 株式会社リコー インクジェット用捺染インク、インクジェット記録装置、及びインクジェット記録方法
WO2019031321A1 (fr) * 2017-08-08 2019-02-14 サカタインクス株式会社 Composition d'encre pour jet d'encre destinée à l'impression textile
JP2019206628A (ja) * 2018-05-29 2019-12-05 東洋インキＳｃホールディングス株式会社 インクジェットインキ及びその印刷物
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