Classifications

• • 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
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • 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
• • 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
• • 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
  • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
  • D06P1/5257—(Meth)acrylic acid
• • 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
  • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
  • D06P1/642—Compounds containing nitrogen
  • D06P1/6426—Heterocyclic compounds
• • 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

• Textile printing is the printing of images or other expressions onto fabrics such as cloth or textile products using ink.
• Patent Document 1 discloses an invention relating to a textile printing method, and describes how by adjusting the heating temperature of the fabric, the amount of ink ejected, and the number of prints, it is possible to easily obtain printed products with excellent wash fastness and friction fastness.
• the present invention aims to provide a new printing ink that can produce a printed item (fabric printed with a printing ink) that exhibits excellent wet friction fastness without requiring ingenuity in the heating temperature of the fabric, the amount of ink ejected, the number of prints, etc., as well as a polymer suitable for the printing ink, and an emulsion containing this polymer.
• a textile printing ink comprising a polymer having a structural unit derived from an ester of (meth)acrylic acid and a secondary alcohol.
• Further comprising an aqueous solvent comprising water and a water-soluble organic solvent The textile printing ink according to [1] or [2], wherein a content ratio of the water-soluble organic solvent in 100 mass% of the aqueous solvent is 10 to 40 mass%.
• [4] The textile printing ink according to any one of [1] to [3], wherein the ester of (meth)acrylic acid and a secondary alcohol includes at least one selected from the group consisting of 2-octyl (meth)acrylate and isobornyl (meth)acrylate.
• [5] The textile printing ink according to any one of [1] to [4], which is for ink-jet textile printing.
• [6] A fabric printed with the textile printing ink according to any one of [1] to [5].
• [7] A polymer for use in a textile printing ink, having a structural unit derived from an ester of (meth)acrylic acid and a secondary alcohol.
• [12] A method of printing using an ink containing a polymer having a structural unit derived from an ester of (meth)acrylic acid and a secondary alcohol. [13] The method according to [12], wherein the content of the polymer in the ink is 1 to 30 mass %. [14] The ink further contains an aqueous solvent comprising water and a water-soluble organic solvent, The method according to [12] or [13], wherein the content of the water-soluble organic solvent in 100% by mass of the aqueous solvent is 10 to 40% by mass. [15] The method according to any one of [12] to [14], wherein the printing is performed by an ink-jet method.
• a method for producing a printed fabric comprising printing an ink containing a polymer having a structural unit derived from an ester of (meth)acrylic acid and a secondary alcohol onto a fabric.
• the ink further contains an aqueous solvent comprising water and a water-soluble organic solvent, The method according to [19] or [20], wherein the content of the water-soluble organic solvent in 100% by mass of the aqueous solvent is 10 to 40% by mass.
• the present invention makes it possible to provide a new printing ink that can produce printed products that exhibit excellent wet rub fastness.
• a to B indicating a numerical range means “A or more, B or less.”
• (meth)acrylic acid means acrylic acid or methacrylic acid
• (meth)acrylate means acrylate or methacrylate.
• the textile printing ink of the present invention is characterized by containing a polymer (hereinafter sometimes referred to as polymer A) having a structural unit derived from an ester of (meth)acrylic acid and a secondary alcohol.
• polymer A is suitable for use in textile printing inks, and the use of this polymer A in textile printing inks is also included in the present invention.
• Polymer A can also be said to be a polymer for textile printing inks, and this polymer for textile printing inks is also included in the present invention.
• the secondary alcohol constituting the ester of (meth)acrylic acid and a secondary alcohol is preferably an alcohol having two aliphatic hydrocarbon groups and one hydrogen atom bonded to a carbon atom directly bonded to a hydroxyl group.
• the two aliphatic hydrocarbon groups bonded to the carbon atom may be bonded to each other at any position to form a ring including the carbon atom.
• the secondary alcohol is preferably an alcohol in which two alkyl groups (groups represented by C n H 2n+1 ) and one hydrogen atom are bonded to a carbon atom directly bonded to a hydroxy group (hereinafter, this may be referred to as a secondary alkyl alcohol), or an alcohol in which a saturated aliphatic hydrocarbon ring is contained in a carbon atom directly bonded to a hydroxy group and one hydrogen atom is bonded to the carbon atom (hereinafter, this may be referred to as a secondary alicyclic alcohol).
• the alkyl group may be linear or branched, but is preferably linear.
• the alkyl group preferably has 1 to 20 carbon atoms, and more preferably has 1 to 12 carbon atoms.
• the saturated aliphatic hydrocarbon ring may be either monocyclic or polycyclic, and preferably has 3 to 18 carbon atoms.
• the secondary alcohol preferably has 3 to 21 carbon atoms, more preferably 4 to 18, and even more preferably 6 to 15.
• An example of an ester of (meth)acrylic acid and a secondary alkyl alcohol is the compound represented by the following formula (b1).
• R 1 represents a hydrogen atom or a methyl group.
• R 2 and R 3 represent an alkyl group, the total number of carbon atoms in the alkyl groups of R 2 and R 3 is 2 to 20, and the number of carbon atoms in R 2 is equal to or less than the number of carbon atoms in R 3. ]
• the alkyl group represented by R2 and R3 may be linear or branched, but is preferably linear.
• alkyl group represented by R2 and R3 include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl groups; and branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 2,3-dimethyl-2-butyl, 3-methylheptyl, and 2-ethylhexyl groups.
• linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-
• the total number of carbon atoms in the alkyl groups of R 2 and R 3 is preferably 3 to 20, more preferably 3 to 15, and even more preferably 5 to 14.
• the alkyl group of R2 preferably has 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and even more preferably 1 carbon atom.
• the alkyl group of R3 preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms.
• esters of (meth)acrylic acid and secondary alkyl alcohols include isopropyl (meth)acrylate, 2-butyl (meth)acrylate, 2-pentyl (meth)acrylate, 3-methyl-2-butyl (meth)acrylate, 3-pentyl (meth)acrylate, 2-hexyl (meth)acrylate, 3,3-dimethyl-2-butyl (meth)acrylate, 3-methyl-2-pentyl (meth)acrylate, 4-methyl-2-pentyl (meth)acrylate, 2,4-dimethyl-3-pentyl (meth)acrylate, 2-heptyl (meth)acrylate, and 2-methyl-3-hexyl.
• esters of (meth)acrylic acid and secondary alicyclic alcohols include esters of (meth)acrylic acid and cycloalkanols (i.e., cycloalkyl (meth)acrylates), such as cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cycloheptyl (meth)acrylate, and cyclooctyl (meth)acrylate; esters of (meth)acrylic acid and secondary polycyclic alcohols, such as isobornyl (meth)acrylate; and the like.
• esters of (meth)acrylic acid and secondary polycyclic alcohols such as isobornyl (meth)acrylate; and the like.
• a compound represented by formula (b1), an ester of (meth)acrylic acid and a cycloalkanol (cycloalkyl (meth)acrylate), or isobornyl (meth)acrylate is preferred, a compound represented by formula (b1) in which R 2 is an alkyl group having 1 to 4 carbon atoms and R 3 is an alkyl group having 4 to 12 carbon atoms, an ester of (meth)acrylic acid and a cycloalkanol having 6 to 10 carbon atoms, or isobornyl (meth)acrylate is more preferred, and 2-octyl (meth)acrylate, cyclohexyl (meth)acrylate, or isobornyl (meth)acrylate is even more preferred.
• the monomer b preferably contains at least a compound represented by formula (b1) and/or an ester of (meth)acrylic acid and a secondary polycyclic alcohol; more preferably contains at least a compound represented by formula (b1) in which R 2 is an alkyl group having 1 to 2 carbon atoms and R 3 is an alkyl group having 4 to 10 carbon atoms and/or isobornyl (meth)acrylate; and further preferably contains at least 2-octyl (meth)acrylate and/or isobornyl (meth)acrylate.
• the total content of the structural units derived from the compound represented by formula (b1) and the structural units derived from an ester of (meth)acrylic acid and a secondary polycyclic alcohol is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and may be 80 to 98% by mass, in 100% by mass of the structural units derived from monomer b.
• the monomer b preferably contains an ester of methacrylic acid and a secondary alcohol; more preferably contains at least a compound in which R 1 in formula (b1) is a methyl group and/or an ester of methacrylic acid and a secondary polycyclic alcohol; further preferably contains at least a compound in which R 1 in formula (b1) is a methyl group, R 2 is an alkyl group having 1 to 2 carbon atoms, and R 3 is an alkyl group having 4 to 10 carbon atoms, and/or isobornyl methacrylate; and still further preferably contains at least 2-octyl methacrylate and/or isobornyl methacrylate.
• the monomer b preferably contains a compound represented by formula (b1), more preferably contains a compound in which R 2 is an alkyl group having 1 to 2 carbon atoms and R 3 is an alkyl group having 4 to 10 carbon atoms in formula (b1), and even more preferably contains 2-octyl(meth)acrylate.
• the content of the structural unit derived from the compound represented by formula (b1) is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, even more preferably 70 to 100 mass%, or may be 80 to 98 mass%, in 100 mass% of the structural units derived from monomer b.
• the monomer b is preferably an ester of a secondary alcohol and (meth)acrylic acid that can be synthesized using a biomass material as a raw material.
• esters of a secondary alcohol and (meth)acrylic acid that can be synthesized using a biomass material as a raw material include 2-octyl (meth)acrylate and isobornyl (meth)acrylate, and among these, 2-octyl (meth)acrylate and isobornyl (meth)acrylate are preferred.
• the total content of structural units derived from esters of secondary alcohols and (meth)acrylic acid preferably 2-octyl (meth)acrylate and isobornyl (meth)acrylate
• biomass materials as raw materials
• the upper limit of the content is not particularly limited, but may be 100% by mass or 95% by mass or less.
• 2-octyl (meth)acrylate can be obtained by cracking ricinoleic acid derived from castor oil collected and extracted from castor seeds, and then esterifying 2-octanol obtained by distilling a mixture containing sebacic acid as a by-product with (meth)acrylic acid.
• isobornyl (meth)acrylate can be obtained by isomerizing ⁇ -pinene obtained from pine resin or pine essential oil to camphene, and then reacting the camphene with (meth)acrylic acid.
• the (meth)acrylic acid used in the production of 2-octyl (meth)acrylate, isobornyl (meth)acrylate, etc. may be derived from either a bio-source or a petroleum-source.
• the structural unit derived from monomer b may be contained in polymer A alone or in two or more types.
• the proportion of structural units derived from monomer b in polymer A is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. It may be 100% by mass, but is preferably 95% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. That is, the proportion of structural units derived from monomer b in polymer A is, for example, 5 to 100% by mass, preferably 10 to 95% by mass, more preferably 15 to 80% by mass, and even more preferably 20 to 70% by mass.
• the polymer A may contain a structural unit derived from a monomer other than the monomer b (hereinafter, sometimes referred to as monomer c).
• monomer c a monomer other than the monomer b
• monomer c there are no particular limitations on the monomer c, and examples thereof include styrene-based monomers, (meth)acrylic acid alkyl esters other than the monomer b, acid group-containing monomers, hydroxyl group-containing monomers, and other monomers, as described below. It is particularly preferable that the monomer c is appropriately selected so that the glass transition temperature of the polymer A is in the range described below.
• polymer A when polymer A contains 50% by mass or more (preferably 55% by mass or more, more preferably 70% by mass or more) of structural units derived from monomer b (hereinafter may be referred to as monomer bL ) having a glass transition temperature of a homopolymer of ⁇ 20° C. or lower (preferably ⁇ 30 to ⁇ 80° C.) out of 100% by mass of structural units derived from monomer b, polymer A preferably contains structural units derived from monomer c (hereinafter may be referred to as monomer cH ) having a glass transition temperature of a homopolymer of 0 to 120° C., together with the structural units derived from monomer bL.
• monomer cH structural units derived from monomer c
• a monomer having a glass transition temperature of a homopolymer of ⁇ 20° C. or lower can be selected from the above-mentioned monomers b, and examples thereof include a compound in which R 1 in formula (b1) is a hydrogen atom and the homopolymer has a glass transition temperature of ⁇ 20° C. or lower.
• 2-octyl acrylate is preferable as the monomer b L.
• the monomer cH include styrene-based monomers and methacrylic acid C 1-5 alkyl esters, which will be described later, and among these, styrene and methyl methacrylate are preferred.
• the total content of the structural units derived from monomer bL and the structural units derived from monomer cH (particularly, the total content of the structural units derived from monomer bL and the structural units derived from at least one monomer selected from a styrene-based monomer and a methacrylic acid C 1-5 alkyl ester) in polymer A is preferably 40 to 100 mass%, more preferably 50 to 95 mass%, and may be 70 to 95 mass% or 85 to 95 mass%.
• polymer A contains more than 50 mass% (preferably 55 mass% or more, more preferably 70 mass% or more) of structural units derived from monomer b (hereinafter, sometimes referred to as monomer b H ) having a glass transition temperature of a homopolymer exceeding -20°C (higher than -20°C) out of 100 mass% of structural units derived from monomer b
• the polymer A preferably contains structural units derived from monomer c (hereinafter, sometimes referred to as monomer c L ) having a glass transition temperature of a homopolymer below 0°C (preferably -80 to -10°C) together with the structural units derived from monomer b H.
• the glass transition temperature of the homopolymer of monomer b H is preferably -10 to 100°C.
• a monomer having a glass transition temperature of a homopolymer exceeding ⁇ 20° C. can be selected from the above-mentioned monomers b, and examples thereof include a compound in which R 1 in formula (b1) is a methyl group and the homopolymer has a glass transition temperature of exceeding ⁇ 20° C., a cycloalkyl methacrylate, isobornyl (meth)acrylate, etc.
• the monomer b H 2-octyl methacrylate, cycloalkyl methacrylate, isobornyl (meth)acrylate are preferred, and 2-octyl methacrylate, isobornyl (meth)acrylate are more preferred.
• Examples of monomer cL include low Tg (meth)acrylic acid alkyl esters described below, and preferred are C 4-10 alkyl acrylates such as n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2 - ethylhexyl acrylate, and n-nonyl acrylate.
• C 4-10 alkyl acrylates such as n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2 - ethylhexyl acrylate, and n-nonyl acrylate.
• the total content of the structural units derived from monomer b H and the structural units derived from monomer c L (particularly, the total content of the structural units derived from monomer b H and the structural units derived from C 4-10 alkyl acrylate) in polymer A is preferably 40 to 100 mass%, more preferably 50 to 95 mass%, and may be 70 to 95 mass%, or 85 to 95 mass%.
• the "glass transition temperature of a homopolymer” may be, for example, a value listed in "POLYMER HANDBOOK THIRD EDITION” (written by J. BRANDRUP and E. H. IMMERGUT, published by John Wiley & Sons, Inc., 1989, pages VI/209 to VI/277) (if multiple Tg values are listed, the lowest value).
• values calculated by computer using commercially available glass transition temperature calculation software for example, “MATERIALS STUDIO” manufactured by Accelrys Software Inc., version: 4.0.0.0, module: Synthia, conditions: calculation with a polymerization average molecular weight of 100,000 may be used.
• the polymer A preferably contains a structural unit derived from a styrene-based monomer.
• the wet rub fastness and washing fastness are further improved.
• styrene-based monomer examples include styrene which may have one or more substituents such as a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (e.g., a C 1-4 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, etc.), a vinyl group, an alkoxysilyl group (e.g., a C 1-4 trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, etc.).
• the substituent is preferably at least one selected from a halogen atom and an alkyl group.
• styrene-based monomer examples include styrene, ⁇ -methylstyrene, p-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, divinylbenzene, p-styryltrimethoxysilane, and 2-styrylethyltrimethoxysilane, with styrene being preferred.
• the structural unit derived from the styrene-based monomer may be contained in polymer A alone or in two or more types.
• the proportion of structural units derived from styrene-based monomers in polymer A is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less.
• the proportion of structural units derived from styrene-based monomers in polymer A is, for example, 0 to 70% by mass, preferably 1 to 70% by mass, more preferably 5 to 60% by mass, even more preferably 10 to 50% by mass.
• the content of the structural units derived from styrene-based monomers is, for example, 0 to 150 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the structural units derived from monomer b.
• the polymer A may contain an alkyl (meth)acrylate ester other than the monomer b.
• (meth)acrylic acid alkyl esters other than monomer b include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, tridecyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, henicosyl (meth)acrylate, t
• (meth)acrylic acid C 1-20 alkyl esters are preferred. Also preferred is at least one selected from (meth)acrylic acid alkyl esters having a homopolymer glass transition temperature (Tg) of ⁇ 20° C. or lower (hereinafter sometimes referred to as low Tg (meth)acrylic acid alkyl esters) and methacrylic acid C 1-5 alkyl esters.
• Tg homopolymer glass transition temperature
• the Tg of the low Tg (meth)acrylic acid alkyl ester is -20°C or lower, preferably -100 to -20°C, and more preferably -80 to -30°C.
• Examples of the low Tg (meth)acrylic acid alkyl ester include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, and isononyl acrylate, and among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.
• the obtained printed material is likely to have an excellent texture.
• the polymer A contains a structural unit derived from an ester of (meth)acrylic acid and a secondary alicyclic alcohol, it is preferable that the polymer A further contains a structural unit derived from a low Tg (meth)acrylic acid alkyl ester.
• the methacrylic acid C1-5 alkyl ester a methacrylic acid C1-3 alkyl ester is preferred, and methyl methacrylate is more preferred.
• the polymer A contains a structural unit derived from a methacrylic acid C1-5 alkyl ester, the wet friction fastness and washing fastness (particularly, washing fastness) are further improved.
• the polymer A contains a structural unit derived from an ester of (meth)acrylic acid and a secondary alkyl alcohol, it is preferred that the polymer A further contains a structural unit derived from a methacrylic acid C1-5 alkyl ester.
• the structural units derived from the (meth)acrylic acid alkyl ester other than monomer b may be contained in polymer A alone or in two or more types.
• polymer A contains structural units derived from (meth)acrylic acid alkyl esters other than monomer b
• the proportion of structural units derived from (meth)acrylic acid alkyl esters other than monomer b in polymer A is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 30% by mass or more, and preferably 85% by mass or less, more preferably 75% by mass or less, even more preferably 65% by mass or less.
• the proportion of structural units derived from (meth)acrylic acid alkyl esters other than monomer b in polymer A is, for example, 0 to 85% by mass, preferably 1 to 85% by mass, more preferably 5 to 75% by mass, even more preferably 15 to 65% by mass, and even more preferably 30 to 65% by mass.
• the content of structural units derived from (meth)acrylic acid alkyl ester other than monomer b is, for example, 0 to 300 parts by mass, preferably 3 to 200 parts by mass, more preferably 30 to 180 parts by mass, and may be 100 to 180 parts by mass, relative to 100 parts by mass of the structural units derived from monomer b.
• the polymer A preferably contains a structural unit derived from a styrene-based monomer and/or a structural unit derived from a methacrylic acid C1-5 alkyl ester, and more preferably contains at least a structural unit derived from a styrene-based monomer.
• the total proportion of the structural units derived from the styrene-based monomer and the methacrylic acid C1-5 alkyl ester in the polymer A is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. That is, the total proportion of the structural units derived from the styrene-based monomer and the methacrylic acid C1-5 alkyl ester in the polymer A is, for example, 0 to 70% by mass, preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass.
• the total content of the structural units derived from the styrene-based monomer and the methacrylic acid C 1-5 alkyl ester is, for example, 0 to 300 parts by mass, preferably 3 to 200 parts by mass, and more preferably 30 to 180 parts by mass, relative to 100 parts by mass of the structural units derived from the monomer b.
• the polymer A further contains a structural unit derived from an acid group-containing monomer.
• the stability of the polymer A is improved, and as a result, the generation of aggregates during polymerization can be suppressed.
• the polymer A contains a structural unit derived from an acid group-containing monomer, it becomes a crosslinking point that reacts with a crosslinking agent described later, and therefore a tough coating film (image) can be formed, and therefore the friction fastness and washing fastness can be further improved.
• the acid group-containing monomer may have at least one acid group and at least one polymerizable unsaturated group in the molecule.
• the acid group include sulfo and carboxy groups, with the carboxy group being preferred.
• Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, cinnamic acid, and crotonic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; monoesters of unsaturated dicarboxylic acids such as maleic acid monomethyl ester, maleic acid monobutyl ester, itaconic acid monomethyl ester, and itaconic acid monobutyl ester; anhydrides of unsaturated dicarboxylic acids such as maleic anhydride; 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-acryloyloxyethyl he
• the structural unit derived from the acid group-containing monomer may be contained in polymer A alone or in two or more types.
• the proportion of structural units derived from acid group-containing monomers in polymer A is preferably 0.1% by mass or more, more preferably 0.5% by mass or more or more than 0.5% by mass, even more preferably 1.0% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. That is, the proportion of structural units derived from acid group-containing monomers in polymer A is, for example, 0 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, even more preferably more than 0.5% by mass and 8% by mass or less, and even more preferably 1.0 to 5% by mass.
• the content of the structural units derived from the acid group-containing monomer is, for example, 0 to 30 parts by mass, preferably 0.5 to 25 parts by mass, more preferably 1.0 to 20 parts by mass, and even more preferably 2.0 to 15 parts by mass, relative to 100 parts by mass of the structural units derived from the monomer b.
• polymer A further contains a structural unit derived from a hydroxyl group-containing monomer.
• the hydroxyl-containing monomer may have at least one hydroxyl group and at least one polymerizable unsaturated group in the molecule.
• Specific examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; halogen-substituted hydroxyalkyl (meth)acrylates such as 3-chloro-2-hydroxypropyl (meth)acrylate; modified hydroxyalkyl (meth)acrylates such as caprolactone-modified 2-hydroxyethyl (meth)acrylate and 2-(meth)acryloyloxyethyl 2-hydroxy
• the structural unit derived from the hydroxyl group-containing monomer may be contained in polymer A alone or in two or more types.
• the proportion of structural units derived from hydroxyl-containing monomers in polymer A is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less.
• the proportion of structural units derived from hydroxyl-containing monomers in polymer A is, for example, 0 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, even more preferably 0.5 to 3% by mass.
• the content of the structural units derived from the hydroxyl group-containing monomer is, for example, 0 to 30 parts by mass, preferably 0.5 to 20 parts by mass, more preferably 1.0 to 15 parts by mass, and even more preferably 0.8 to 8 parts by mass, relative to 100 parts by mass of the structural units derived from the monomer b.
• the polymer A may further have a structural unit derived from a monomer other than the above-mentioned monomers (monomer b, acid group-containing monomer, hydroxyl group-containing monomer, styrene-based monomer, and (meth)acrylic acid alkyl ester).
• the other monomer may be a monomer other than the above-mentioned monomers and have at least one polymerizable unsaturated group in the molecule (excluding reactive emulsifiers described later).
• the other monomers include: Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, and octafluoropentyl (meth)acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate and naphthyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate, phenylethyl (meth)acrylate, methylbenzyl (meth)acrylate, and naphthylmethyl (meth)acrylate; alkoxyalkyl group-containing (meth)acrylates such as methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxybutyl (meth)acrylate, and trimethylolpropane tripropoxy (meth)acrylate; Carbonyl group-containing (meth)
• the structural units derived from other monomers may be contained in the copolymer either alone or in combination of two or more types.
• the proportion of structural units derived from other monomers in polymer A is, for example, 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and may be 5 or 3% by mass or less.
• the proportion of structural units derived from other monomers in the copolymer may be 0% by mass or more, 0.5% by mass or more, or 1% by mass or more.
• the proportion of structural units derived from other monomers in polymer A may be 0-50% by mass, 0-30% by mass, 0-10% by mass, 0.5-5% by mass, or 1-3% by mass.
• the weight average molecular weight (Mw) of polymer A is preferably 50,000 or more, more preferably 300,000 or more, further preferably 550,000 or more, and particularly preferably 600,000 or more.
• the upper limit of the weight average molecular weight of polymer A is preferably 5,000,000 or less.
• the dispersity (Mw/Mn) of polymer A is preferably 10.0 or less, more preferably 8.0 or less, and even more preferably 6.0 or less.
• the lower limit of the dispersity is preferably 1, and may be 2 or 3. That is, the dispersity (Mw/Mn) of polymer A is preferably 1 to 10.0, more preferably 2 to 8.0, and even more preferably 3 to 6.0.
• the weight average molecular weight and number average molecular weight can be calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC).
• the glass transition temperature (Tg (°C)) of polymer A is not particularly limited, but from the viewpoint that a printed product obtained using the textile printing ink of the present invention is likely to have excellent texture, it is preferably 10°C or lower, more preferably 5°C or lower, and even more preferably 3°C or lower.
• the lower limit is not particularly limited, but is preferably -50°C or higher, and more preferably -40°C or higher.
• the Tg of polymer A is preferably -50 to 10°C, more preferably -40 to 5°C, and even more preferably -40 to 3°C.
• the Tg (° C.) of polymer A can be measured by differential scanning calorimetry (AST D3418-08), but may also be calculated from Tg A (K) calculated from the Fox equation shown in the following formula (1).
• Tg A is Tg(K) of polymer A
• Tg n is Tg(K) of a homopolymer of each monomer used
• W n is the blending ratio (mass%) of each monomer to the total monomer components used.
• the polymer A can be obtained by polymerizing the above-mentioned monomer b, and an acid group-containing monomer, a hydroxyl group-containing monomer, a styrene-based monomer, an (meth)acrylic acid alkyl ester, and other monomers (hereinafter, these monomers are collectively referred to as monomer components) that are used as necessary.
• a known polymerization method can be adopted, for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, etc. are included.
• a solution polymerization method or an emulsion polymerization method is preferable.
• the type, combination, and compounding ratio of the preferred monomer components used in each polymerization method are in accordance with the preferred form described for the monomer for forming the above-mentioned polymer A.
• a preferred production method will be described in detail below, but is not limited thereto.
• any method can be used, such as a method in which the monomer components are charged all at once and polymerized, a method in which the monomer components are polymerized while being added dropwise, or a method in which some of the monomer components are charged all at once and the remaining monomer components are polymerized while being added dropwise.
• the monomer components are charged all at once and polymerized, it is more preferable to charge a polymerization initiator together with the monomer components so that a polymer A having a high molecular weight can be produced.
• the monomer components are polymerized while being added dropwise, it is more preferable to add a mixture of the monomer components and the polymerization initiator dropwise in order to keep the ratio of the monomer components to the polymerization initiator as constant as possible.
• polymerization initiators used in the solution polymerization method include peroxide-based polymerization initiators such as methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, t-butyl peroxybenzoate, and lauroyl peroxide; and azo-based polymerization initiators such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine).
• the polymerization initiators may be used alone or in combination of two or more.
• the amount of polymerization initiator used in the solution polymerization method is preferably 0.01 to 3 parts by mass per 100 parts by mass of the monomer components. If the amount of polymerization initiator exceeds 3 parts by mass, it may not be possible to obtain polymer A with the desired weight average molecular weight.
• the solvent used in the solution polymerization method is preferably an organic solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, cyclooctane, ⁇ -pinene, terpinolene, and limonene; aromatic hydrocarbon solvents such as toluene, xylene, benzene, and solvent naphtha; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone
• solvents may be used alone or in combination of two or more.
• the amount of solvent used may be determined appropriately depending on the reaction conditions, the composition of the monomer components, etc., so that a polymer A with the desired physical properties is obtained.
• the amount of solvent used is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 30 to 100 parts by mass, per 100 parts by mass of the monomer components.
• the reaction conditions in the solution polymerization method are not particularly limited. Specifically, they can be appropriately determined depending on the composition of the monomer components and the properties required for the resulting polymer A, and the like.
• the reaction temperature is, for example, 0 to 100°C, preferably 50 to 95°C, and more preferably 60 to 90°C
• the reaction time is, for example, 0.5 to 30 hours, preferably 1 to 20 hours, and more preferably 3 to 10 hours.
• the reaction pressure is also not particularly limited, and may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure. It is desirable to carry out the polymerization reaction under an atmosphere of an inert gas such as nitrogen gas.
• a preferred example is a method in which the monomer components are emulsion-polymerized in an aqueous solvent in the presence of an emulsifier and a polymerization initiator.
• the specific means and conditions for carrying out the emulsion polymerization can be appropriately selected and adopted from the means and techniques in conventionally known emulsion polymerization methods.
• the emulsifier used in carrying out the emulsion polymerization is not limited, but may be a nonionic emulsifier, anionic emulsifier, cationic emulsifier, amphoteric emulsifier, etc., and any emulsifier known in the art may be used. Each of these emulsifiers may be used alone, or two or more of them may be used in combination. Among the above emulsifiers, nonionic emulsifiers or anionic emulsifiers are preferred. Emulsifiers containing a polymerizable group in the molecule (also called reactive emulsifiers) are also preferred.
• a reactive emulsifier As an emulsifier, a structural unit derived from the reactive emulsifier is introduced into the polymer A. Therefore, it is preferred that the polymer A contains a structural unit derived from the reactive emulsifier.
• the above emulsifiers nonionic emulsifiers containing a polymerizable group or anionic emulsifiers containing a polymerizable group are particularly preferred.
• Polymeric emulsifiers can also be used as emulsifiers.
• Anionic emulsifiers include, for example, alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate and sodium alkyl diphenyl ether disulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl ether sulfate salts; polyoxyethylene alkyl aryl ether sulfate salts; dialkyl sulfosuccinate salts; aryl sulfonic acid-formaldehyde.
• Condensates fatty acid salts such as ammonium laurate and sodium stearylate; sulfates or salts thereof having an allyl group such as bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salts, propenyl-alkyl sulfosuccinate salts, polyoxyethylene (meth)acrylate sulfonate salts, polyoxyethylene (meth)acrylate phosphonate salts, and sulfonate salts of allyloxymethyl alkyloxy polyoxyethylene; sulfate salts of allyloxymethyl alkoxyethyl polyoxyethylene; and polyoxyalkylene alkenyl ether ammonium sulfate salts; but are not limited to these examples.
• fatty acid salts such as ammonium laurate and sodium stearylate
• sulfates or salts thereof having an allyl group such as bis(polyoxyethylene polycyclic phenyl
• Nonionic emulsifiers include, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, condensation products of polyethylene glycol and polypropylene glycol, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensation products of ethylene oxide and aliphatic amines, polyoxyalkylene alkenyl ethers, etc., but are not limited to these examples.
• polymeric emulsifiers examples include poly(meth)acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl(meth)acrylates such as polyhydroxyethyl acrylate; and copolymers in which one or more of the monomers constituting these polymers are copolymerization components; but are not limited to these examples.
• the reactive emulsifier refers to an emulsifier having a polymerizable group, a hydrophilic group, and a hydrophobic group, and may have one or more polymerizable groups in one molecule.
• the polymerizable group is preferably a group having an ethylenically unsaturated double bond, and specific examples thereof include a (meth)acryloyl group, a vinyl group, an allyl group, and a styryl group.
• Examples of the hydrophilic group include groups known as emulsifiers (surfactants).
• anionic groups such as a sulfonic acid group, a phosphoric acid group, a sulfate ester residue, and a phosphoric acid ester residue; and nonionic groups such as a polyether group and an ester group are preferred.
• the hydrophobic group may also be a group known as an emulsifier (surfactant).
• Preferred examples of the hydrophobic group include an alkyl group (particularly an alkyl group having about 8 to 40 carbon atoms), an aryl group-containing hydrocarbon group (particularly a phenyl group-containing hydrocarbon group having about 12 to 40 carbon atoms), and a polycyclic phenyl group.
• reactive emulsifiers include: Propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, (meth)acrylic acid polyoxyethylene phosphonate salts (e.g., Sanyo Chemical Industries, Ltd., product name: ELEMINOL RS-30, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: AQUALON HS-10, etc.), allyloxymethyl alkyloxy polyoxyethylene sulfonate salts (e.g., Daiichi Kogyo Seiyaku Co., Ltd., product name: AQUALON KH-10, etc.), polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salts, anionic emulsifiers having
• the amount of the emulsifier used is not limited, but is, for example, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less, and is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of the monomer components. That is, the amount of the emulsifier used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the monomer components. If necessary, protective colloids can be used alone or together with an emulsifier.
• the polymerization initiator used in carrying out the above emulsion polymerization includes, but is not limited to, azo-based polymerization initiators such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; peroxide-based polymerization initiators such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide; and the like, but is not limited to these examples. Each of these polymerization initiators may be used alone, or two or more types may be used in combination.
• the amount of polymerization initiator used in carrying out the above emulsion polymerization is preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the monomer components.
• a peroxide-based polymerization initiator as the polymerization initiator, if it is necessary to increase the polymerization rate or lower the reaction temperature, a reducing agent such as a soluble sulfite or ascorbic acid, or a metal compound such as ferrous sulfate that generates heavy metal ions in water, can be combined with the peroxide-based polymerization initiator to form a redox-based initiator.
• the reaction temperature during the emulsion polymerization can be set appropriately taking into consideration the weight-average molecular weight of the resulting polymer A, the blending ratio of the monomer components, and the type of polymerization initiator, but the reaction temperature is, for example, 0 to 100°C, preferably 50 to 95°C, and more preferably 60 to 90°C, and the reaction time is, for example, 0.5 to 30 hours, preferably 1 to 20 hours, and more preferably 3 to 10 hours.
• the reaction pressure There are no particular limitations on the reaction pressure, and it may be normal pressure (atmospheric pressure), reduced pressure, or increased pressure.
• the polymerization reaction is desirably carried out in an atmosphere of an inert gas such as nitrogen gas.
• the aqueous solvent used in the emulsion polymerization may be water or a mixture of water and a water-soluble organic solvent.
• the water content in the aqueous solvent is preferably 10 to 100% by mass, more preferably 25% by mass or more, even more preferably 60% by mass or more, and particularly preferably 90% by mass or more.
• the remainder is preferably a water-soluble organic solvent.
• water-soluble organic solvent examples include: Lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and tert-butyl alcohol; Dihydric alcohols (preferably glycols) such as propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; Trihydric alcohols such as glycerin; Ethers of monoethylene glycol, such as monoethylene glycol monomethyl ether, monoethylene glycol monoethyl ether, monoethylene glycol monopropyl ether, monoethylene glycol monoisopropyl ether, monoethylene glycol monobutyl ether, and monoethylene glycol monoisobutyl ether; Ethers of monopropylene glycol, such as monopropylene glycol monomethyl ether, monopropylene glycol monoethyl
• the amount of aqueous solvent used when carrying out the above emulsion polymerization is not limited, but is preferably 20 to 300 parts by mass, more preferably 30 to 200 parts by mass, and even more preferably 40 to 150 parts by mass, per 100 parts by mass of the monomer components.
• polymerization method in the above emulsion polymerization include monomer drop polymerization, pre-emulsion drop polymerization, seed polymerization, and multi-stage polymerization.
• additives such as chain transfer agents, such as compounds having a thiol group, such as tert-dodecyl mercaptan, pH buffers, and chelating agents, may be added in appropriate amounts to the reaction system in the above emulsion polymerization.
• the amount of additive varies depending on the type and cannot be determined in general, but is usually preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer components.
• an emulsion is obtained in which the obtained polymer A is dispersed in an aqueous solvent as emulsion particles.
• polymer A is added to the textile printing ink of the present invention, it is preferable to add it as an emulsion, that is, polymer A is preferably included as emulsion particles in the textile printing ink of the present invention.
• the emulsion for textile printing ink and the use of the emulsion in textile printing ink are also included in the present invention. The emulsion for textile printing ink of the present invention will be described in detail below.
• the emulsion particles contained in the emulsion for a textile printing ink of the present invention are emulsion particles constituted by the above-mentioned polymer A, that is, the emulsion for a textile printing ink of the present invention contains the above-mentioned polymer A.
• the composition and physical properties of the polymer A constituting the emulsion particles are as described above, and the preferred embodiments are also the same.
• the content of the emulsion particles in the emulsion of the present invention is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and even more preferably 30 to 65% by mass.
• the shape of the emulsion particles is not particularly limited, but is usually spherical. The shape can be measured using a transmission electron microscope or a scanning electron microscope.
• the emulsion particles may have a single-layer structure or a multi-layer structure (e.g., a core-shell structure).
• the average particle size (volume basis) of the emulsion particles is preferably 50 nm or more, more preferably 100 nm or more, and even more preferably 150 nm or more, and is preferably 500 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. That is, the average particle size of the emulsion particles is preferably 50 to 500 nm, more preferably 100 to 350 nm, and even more preferably 150 to 300 nm. By adjusting the average particle size within the above range, it becomes easy to blend the emulsion particles at a high concentration while maintaining the viscosity of the ink within an appropriate range.
• the average particle size (volume basis) of the emulsion particles may be the cumulant average particle size measured by a dynamic light scattering method as shown in the examples described later.
• the aqueous solvent that is the dispersion medium for the emulsion particles may be a solvent derived from the aqueous solvent used during emulsion polymerization, or may be a solvent that is added separately to the reaction liquid of emulsion polymerization or to the isolated polymer A.
• the aqueous solvent include the same aqueous solvents as those described as solvents used in emulsion polymerization.
• the content of the aqueous solvent in the emulsion of the present invention is preferably 30 to 900 parts by mass, more preferably 50 to 400 parts by mass, and even more preferably 70 to 250 parts by mass, per 100 parts by mass of emulsion particles.
• the emulsion particles are preferably dispersed and stabilized with an emulsifier (surfactant).
• an emulsifier surfactant
• examples of the emulsifier include those described as emulsifiers used in emulsion polymerization, and the preferred embodiments are also the same.
• the emulsion obtained by emulsion polymerization usually contains the emulsifier used in the emulsification, but the emulsion may be used as it is as an emulsion for textile printing ink.
• the emulsion may contain additives such as chain transfer agents, such as compounds having a thiol group, such as tert-dodecyl mercaptan, pH buffers, and chelating agents.
• chain transfer agents such as compounds having a thiol group, such as tert-dodecyl mercaptan, pH buffers, and chelating agents.
• the amount of additive varies depending on the type and cannot be determined in general, but is usually preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of emulsion particles.
• the textile printing ink of the present invention contains the polymer A (preferably the emulsion particles).
• the compositions, physical properties, and the like of the polymer A and the emulsion particles contained in the textile printing ink of the present invention are as described above, and preferred embodiments thereof are also as described above.
• the content of the polymer A (preferably the emulsion particles) in the textile ink may be set according to the properties required for the textile ink, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, and is preferably 30% by mass or less, and more preferably 20% by mass or less.
• the content of the polymer A (preferably the emulsion particles) in the textile ink is preferably 1 to 30% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass.
• the content of the polymer A (preferably the emulsion particles) in the solid content (non-volatile content) of the textile ink is preferably 4% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and even more preferably 40% by mass or more. It may be 100% by mass, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
• the content of the polymer A (preferably the emulsion particles) in the solid content of the textile ink is preferably 4 to 100% by mass, more preferably 20 to 95% by mass, even more preferably 30 to 90% by mass, and even more preferably 40 to 85% by mass.
• the content of the polymer A (preferably the emulsion particles) is preferably 4 to 100% by mass, more preferably 20 to 95% by mass, even more preferably 30 to 90% by mass, and even more preferably 40 to 85% by mass.
• the solid content non-volatile content refers to the components excluding the solvent.
• the textile printing ink of the present invention may further contain a crosslinking agent. It is presumed that the use of a crosslinking agent can form a crosslinked structure through interaction with the components contained in the ink of the present invention, such as the polymer A, the pigment, or the pigment dispersant, or through a chemical reaction, and thus form a tough coating film, thereby improving the abrasion fastness and washing fastness.
• crosslinking agent examples include isocyanate compounds, epoxy compounds, melamine compounds, metal chelate compounds, aziridine compounds, mercapto compounds, oxazoline compounds, etc., and preferably oxazoline compounds.
• the crosslinking agent may be used alone or in combination of two or more types.
• the oxazoline compound as the crosslinking agent refers to a compound having two or more oxazoline groups in the molecule.
• the oxazoline compound include 2,2'-bis(2-oxazoline), 2,2'-methylene-bis(2-oxazoline), 2,2'-ethylene-bis(2-oxazoline), 2,2'-trimethylene-bis(2-oxazoline), 2,2'-tetramethylene-bis(2-oxazoline), 2,2'-hexamethylene-bis(2-oxazoline), 2,2'-octamethylene-bis(2-oxazoline), 2,2'-ethylene-bis(4 ,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(2-oxazoline), 2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline), bis(2-oxazolinylcyclohex
• oxazoline compounds water-soluble oxazoline compounds are preferred from the viewpoint of excellent crosslinking performance, and oxazoline group-containing polymers are also preferred.
• the above oxazoline group-containing polymers can be produced by a conventionally known production method. For example, a method of polymerizing a monomer component containing one or more types of addition polymerizable oxazolines, or an addition polymerizable oxazoline and a monomer copolymerizable with the addition polymerizable oxazoline, can be mentioned.
• the copolymerizable monomer a monomer that does not have a functional group that reacts with the oxazoline group and is copolymerizable with the addition polymerizable oxazoline is preferred.
• the above monomer component can include a monomer that does not have a functional group that reacts with the oxazoline group.
• monomer b (meth)acrylic monomers such as (meth)acrylic acid alkyl esters; styrene-based monomers such as styrene, ⁇ -methylstyrene, and chloromethylstyrene; vinyl-based monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate; acrylonitrile; (meth)acrylamide-based monomers such as acrylamide; olefin-based monomers such as ethylene and propylene.
• (meth)acrylic monomers such as (meth)acrylic acid alkyl esters
• styrene-based monomers such as styrene, ⁇ -methylstyrene, and chloromethylstyrene
• vinyl-based monomers such as vinyl acetate, vinyl chloride, and vinyl benzoate
• acrylonitrile (meth)acrylamide-based monomers such as acrylamide
• olefin-based monomers such as ethylene and prop
• Examples of the above-mentioned addition-polymerizable oxazolines include compounds having a polymerizable unsaturated group and an oxazoline group in the molecule, such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline.
• 2-vinyl-2-oxazoline 2-vinyl-4-methyl-2-oxazoline
• 2-vinyl-5-methyl-2-oxazoline 2-isopropenyl-2-oxazoline
• 2-isopropenyl-4-methyl-2-oxazoline 2-isopropenyl-5-methyl-2-oxazoline
• water-soluble oxazoline group-containing polymers are preferred, and can be produced by the same method as the above-mentioned method for producing oxazoline group-containing polymers.
• water-soluble oxazoline group-containing polymers include polymers that have an acrylic polymer, an acrylic-styrene polymer, or the like as the main chain and contain oxazoline groups in the side chains.
• oxazoline group-containing polymers examples include water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., and emulsion-type polymers such as Epocross K-2010, Epocross K-2020, and Epocross K-2030. Of these, water-soluble polymers such as Epocross WS-500 and Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., are preferred.
• the content of the crosslinking agent (preferably an oxazoline compound) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the polymer A. If the amount of the crosslinking agent is within this range, sufficient crosslinking can be achieved, and the friction fastness and/or washing fastness (particularly washing fastness) can be further improved.
• the textile printing ink of the present invention may further contain a pigment.
• a pigment By containing a pigment, the textile printing ink can be made into a white ink or a colored ink. Note that, when the textile printing ink of the present invention is used as a clear ink, it is not necessary to contain a pigment.
• the pigments include organic pigments and inorganic pigments, which may be used alone or in combination of two or more kinds. If necessary, they may also be used in combination with an extender pigment.
• organic pigments examples include azo pigments such as benzidine and Hansa Yellow, diazo pigments, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, iminoisoindoline pigments, isoindolinone pigments such as iminoisoindolinone, dioxazine pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavanthrone pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diarylide yellow, benzimidazolone yellow, tolyl orange, naphthol orange, and quinophthalone pigments.
• azo pigments such as benzidine and Hansa Yellow
• diazo pigments such as benzidine and Hans
• the hue is not particularly limited, and any chromatic pigment such as yellow, magenta, cyan, blue, red, orange, or green can be used. Specific examples include products with product numbers such as C.I. Pigment Yellow, C.I. Pigment Red, C.I. Pigment Orange, C.I. Pigment Violet, C.I. Pigment Blue, and C.I. Pigment Green.
• inorganic pigments examples include titanium dioxide, antimony trioxide, zinc oxide such as zinc oxide, lithopone, white lead, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, and lead chromate.
• inorganic pigments include flat pigments such as mica, clay, aluminum powder, talc, and aluminum silicate, as well as extender pigments such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, and magnesium carbonate.
• carbon black examples include furnace black, thermal lamp black, acetylene black, and channel black.
• preferred white pigments are titanium dioxide, antimony trioxide, zinc oxide such as zinc oxide, lithopone, white lead, calcium carbonate, magnesium hydroxide, aluminum hydroxide, barium sulfate, magnesium carbonate, clay, talc, and aluminum silicate.
• titanium dioxide is preferred from the viewpoint of its high refractive index and excellent hiding power.
• titanium dioxide with a rutile crystal structure is preferred.
• Preferred color pigments include the above organic pigments, red iron oxide, black iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferric ferrocyanide (Prussian blue), ultramarine, lead chromate, etc.
• the average particle size (volume basis) of the pigment is preferably from 10 to 1,000 nm, more preferably from 20 to 500 nm, from the viewpoints of dispersion stability, color development, and hiding power.
• the average particle size (volume basis) is preferably 100 to 500 nm from the viewpoint of superior hiding power
• the lower limit is more preferably 150 nm or more, and even more preferably 200 nm or more
• the upper limit is more preferably 450 nm or less, and even more preferably 400 nm or less. That is, the average particle size (volume basis) of the white pigment is preferably 100 to 500 nm, more preferably 150 to 450 nm, and even more preferably 200 to 400 nm.
• the average particle size (volume basis) is preferably 20 to 200 nm, particularly from the viewpoint of color development, with the lower limit being more preferably 40 nm or more, and even more preferably 50 nm or more, and the upper limit being more preferably 150 nm or less, and even more preferably 100 nm or less. That is, the average particle size (volume basis) of the color pigment is preferably 20 to 200 nm, more preferably 40 to 150 nm, and even more preferably 50 to 100 nm.
• the average particle size of the pigment refers to the average particle size in the printing ink of the present invention.
• the average particle size of the pigment can be measured by a laser diffraction scattering type particle size distribution meter or dynamic light scattering.
• the cumulant average particle size measured by dynamic light scattering can be used, as shown in the examples described later.
• the 50% particle size in the volume-based particle size distribution measured by a laser diffraction scattering type particle size distribution meter can be used as the average particle size.
• the pigment is stabilized in dispersion by a dispersant in the printing ink of the present invention.
• the dispersant include poly(meth)acrylic acid (salts) such as poly(meth)acrylic acid and poly(meth)acrylate salts; copolymers of (meth)acrylic acid (salts) with one or more of the monomer components other than (meth)acrylic acid (salts) such as (meth)acrylic acid alkyl esters, (meth)acrylamide, styrene, maleic acid, maleic anhydride, maleic acid esters, and vinyl acetate; polyvinyl alcohol; and polyvinylpyrrolidone.
• the content of the pigment in the solid content of the textile printing ink is preferably from 5 to 80% by mass, and more preferably from 10 to 75% by mass.
• the content of the white pigment in the solid content of the textile ink is preferably 20 to 80 mass %, and more preferably 35 to 65 mass %
• the content of the organic pigment in the solid content of the textile ink is preferably 5 to 40 mass %, and more preferably 10 to 30 mass %.
• the printing ink of the present invention preferably further contains a solvent.
• the solvent acts as a diluent for adjusting the viscosity of the printing ink.
• an organic solvent or an aqueous solvent can be suitably used as the solvent.
• a printing ink containing an organic solvent as a main component as a solvent may be referred to as a solvent-based printing ink
• a printing ink containing an aqueous solvent as a main component as a solvent may be referred to as an aqueous printing ink.
• the printing ink of the present invention is preferably an aqueous printing ink.
• the printing ink of the present invention may contain one type of solvent alone or two or more types of solvents.
• the content of the organic solvent in the solvent contained in the solvent-based textile printing ink is preferably 70% by mass or more, more preferably 85% by mass or more, and even more preferably 95 or 98% by mass or more, and may be 100% by mass.
• the content of the aqueous solvent in the solvent contained in the aqueous textile printing ink is preferably 70% by mass or more, more preferably 85% by mass or more, and even more preferably 95 or 98% by mass or more, and may be 100% by mass.
• the organic solvent may be a solvent derived from the organic solvent used during solution polymerization, or may be a solvent added separately to the reaction liquid of the solution polymerization or to the isolated polymer A.
• the aqueous solvent may be a solvent derived from the aqueous solvent used during emulsion polymerization, or may be a solvent added separately to the reaction liquid of the emulsion polymerization or to the isolated polymer A.
• Examples of the organic solvent include the same organic solvents as those described above as the solvent used in the solution polymerization method.
• Examples of the aqueous solvent include the same aqueous solvents as those described above as the solvent used in the emulsion polymerization method.
• the textile printing ink of the present invention is an aqueous textile printing ink
• the aqueous solvent contained in the aqueous textile printing ink contains a water-soluble organic solvent together with water.
• the content of the water-soluble organic solvent in the aqueous solvent is preferably 10 to 40% by mass, and more preferably 15 to 30% by mass.
• the water-soluble organic solvent is preferably a water-soluble organic solvent having a boiling point of 150° C. or higher, more preferably a water-soluble organic solvent having a boiling point of 180° C. or higher, and even more preferably a water-soluble organic solvent having a boiling point of 200° C. or higher.
• the water-soluble organic solvent having a boiling point of 150° C. or higher glycol or glycerin having a boiling point of 150° C. or higher is preferred, and specific examples thereof include propylene glycol, diethylene glycol, triethylene glycol, and glycerin.
• the content of the water-soluble organic solvent that further enhances the moisture retention is preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, relative to 100 parts by mass of water in the aqueous solvent.
• the water-soluble organic solvent is preferably a water-soluble organic solvent having a hydrophobic group and a hydroxyl group.
• the hydrophobic group may be a monovalent hydrocarbon group having 3 or more carbon atoms, preferably a monovalent hydrocarbon group having 3 to 8 carbon atoms, more preferably an alkyl group having 3 to 8 carbon atoms, and even more preferably an alkyl group having 3 to 4 carbon atoms.
• the content of the water-soluble organic solvent that further enhances the compatibility is preferably 1 to 15 parts by mass, and more preferably 2 to 8 parts by mass, per 100 parts by mass of water in the aqueous solvent.
• the amount of solvent contained in the printing ink can be set according to the desired viscosity of the printing ink and is not particularly limited, but from the viewpoint of ease of handling, it is, for example, 40 to 90% by mass, preferably 50 to 88% by mass, and more preferably 55 to 85% by mass.
• the textile printing ink of the present invention may further contain additives within the scope of not impairing the object of the present invention.
• additives such as surfactants, dispersants, leveling agents, UV absorbers, UV stabilizers, thickeners, wetting agents, plasticizers, stabilizers, defoamers, dyes, antioxidants, crosslinking accelerators, pH adjusters, and preservatives may be contained in appropriate amounts.
• leveling agent for example, acetylene glycol-based, silicone-based, and fluorine-based surfactants are preferably used, and among them, polyether-modified silicone compounds are preferred.
• the content of the additives in the textile printing ink of the present invention is preferably 0.01 to 2% by mass, and more preferably 0.05 to 1% by mass.
• the textile printing ink of the present invention may further contain a binder resin other than polymer A, such as a vinyl resin, a (meth)acrylic resin other than polymer A, an olefin resin, a urethane resin, a fluorine resin, a silicone resin, an epoxy resin, a phenoxy resin, a phenol resin, or a xylene resin, within the scope of the present invention.
• the polymer A is also included in the binder resin in the textile printing ink.
• the textile printing ink of the present invention may contain one type of binder resin other than polymer A alone, or may contain two or more types.
• a (meth)acrylic resin other than the polymer A hereinafter, sometimes referred to as a (meth)acrylic resin B) is preferable.
• the (meth)acrylic resin B contains structural units derived from low Tg (meth)acrylic acid alkyl esters.
• Examples of the low Tg (meth)acrylic acid alkyl esters are the same as those described above, and the preferred embodiments are also the same.
• the proportion of structural units derived from low Tg (meth)acrylic acid alkyl esters in the (meth)acrylic resin B is preferably 20 to 90% by mass, more preferably 30 to 75% by mass, and even more preferably 40 to 65% by mass.
• the (meth)acrylic resin B preferably further contains a structural unit derived from a styrene-based monomer and/or a methacrylic acid C1-5 alkyl ester, and more preferably contains a structural unit derived from a styrene-based monomer.
• a structural unit derived from a styrene-based monomer and/or a methacrylic acid C1-5 alkyl ester preferably contains a structural unit derived from a styrene-based monomer.
• the styrene-based monomer and the methacrylic acid C1-5 alkyl ester are the same as those described above, and preferred embodiments thereof are also the same.
• the total proportion of the structural units derived from the styrene-based monomer and the methacrylic acid C1-5 alkyl ester in the (meth)acrylic resin B is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.
• the (meth)acrylic resin B may further have structural units derived from an acid group-containing monomer.
• Examples of the acid group-containing monomer are the same as those described above, and the preferred embodiments are also the same.
• the proportion of the structural units derived from the acid group-containing monomer in the (meth)acrylic resin B is preferably 0.1 to 10 mass%, more preferably 0.5 to 8 mass%, and even more preferably 1.0 to 5 mass%.
• the (meth)acrylic resin B may further have structural units derived from hydroxyl-containing monomers.
• Examples of the hydroxyl-containing monomers are the same as those described above, and the preferred embodiments are also the same.
• the proportion of structural units derived from hydroxyl-containing monomers in the (meth)acrylic resin B is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and even more preferably 0.5 to 3% by mass.
• the total content of structural units derived from the low Tg (meth)acrylic acid alkyl ester, the styrene-based monomer, the methacrylic acid C1-5 alkyl ester, the acid group-containing monomer, and the hydroxyl group-containing monomer is preferably 50 to 100 mass %, more preferably 80 mass % or more, and even more preferably 95 mass % or more.
• the content of the polymer A in 100% by mass of the binder resin contained in the textile printing ink of the present invention is, for example, 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, or may be 100% by mass.
• the total content of the polymer A and the (meth)acrylic resin B in 100% by mass of the binder resin contained in the textile printing ink of the present invention is, for example, 50 to 100% by mass, preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more.
• the textile printing ink of the present invention can be particularly suitably used for inkjet textile printing, that is, the textile printing ink of the present invention is preferably for use in inkjet textile printing.
• the method for producing the textile printing ink of the present invention is not particularly limited, and the textile printing ink may be prepared from polymer A or an emulsion containing polymer A.
• the textile printing ink may be produced by mixing polymer A, and a solvent, a crosslinking agent, a pigment, a binder resin other than polymer A, and other additives that are used as necessary.
• An example of a method for producing a water-based textile printing ink that is a preferred embodiment is shown below, but the invention is not limited thereto.
• an emulsion containing polymer A and, if necessary, a pigment dispersion and a dispersion of a binder resin other than polymer A.
• polymer A can be contained in the printing ink as emulsion particles.
• the emulsion containing polymer A the emulsion described above as the emulsion for the printing ink can be used.
• the emulsion can be produced by a conventional emulsion polymerization method as described above.
• the dispersion of the binder resin other than polymer A is preferably an emulsion in which the binder resin other than polymer A is dispersed as emulsion particles in an aqueous solvent.
• the emulsion can be the same as the emulsion of polymer A, except that the resin composition is changed.
• the pigment dispersion is preferably one in which the pigment is dispersed in an aqueous solvent.
• the pigment dispersion can be produced, for example, by mixing the pigment and a dispersant in an aqueous solvent such as water, and dispersing the mixture in a bead mill or the like.
• the dispersant can be the same as the dispersant described above.
• the pigment content in the pigment dispersion is not particularly limited, but is preferably 5 to 65% by mass relative to 100% by mass of the pigment dispersion.
• the white pigment content in the pigment dispersion is preferably 20 to 65% by mass, and more preferably 30 to 60% by mass.
• the organic pigment content in the pigment dispersion is preferably 5 to 40% by mass, and more preferably 8 to 30% by mass.
• the above emulsion and, if necessary, a pigment dispersion, a dispersion of a binder resin other than polymer A, a solvent, a crosslinking agent, and other additives are mixed.
• the above crosslinking agent and other additives may be used as the compound as is, or may be added as a solution diluted with a solvent or the like. There are no particular limitations on the method or order in which the above components are mixed. After mixing, centrifugation, filtration, etc. can be performed as necessary.
• the present invention also includes a fabric printed with the above-mentioned textile printing ink.
• the composition and physical properties of the textile printing ink used for printing the fabric are as described above, and the preferred embodiments are also the same.
• the fabric printed with the above-mentioned textile printing ink may be referred to as a printed item.
• the fabric includes all textile products such as cloth and textiles that use natural and/or synthetic fibers as raw yarn.
• Examples of fabric include woven fabric, nonwoven fabric, and knitted fabric.
• the fibers that make up the fabric are not particularly limited, and examples include natural fibers, chemical fibers, and mixtures of these.
• Preferred examples of natural fibers include silk, cotton, and wool.
• Chemical fibers include synthetic fibers, regenerated fibers, and semi-synthetic fibers.
• Preferred examples of synthetic fibers include polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, and vinylon fibers.
• Preferred examples of regenerated fibers include rayon.
• Preferred examples of semi-synthetic fibers include acetate and triacetate. Of these, fabrics containing at least one of cotton, polyester fibers, and polypropylene fibers are preferred.
• the present invention also includes a method of printing using the above-mentioned printing ink (i.e., the ink containing the above-mentioned polymer A).
• printing refers to printing the ink onto a fabric
• the present invention also includes a method of producing a printed fabric (printed item) by printing the above-mentioned printing ink (i.e., the ink containing the above-mentioned polymer A) onto a fabric.
• the composition and physical properties of the printing ink and the polymer A contained in the printing ink used in the above-mentioned printing method and method of producing a printed item are as described above, and the preferred embodiments are also the same.
• the method for printing the textile ink of the present invention onto fabric is not particularly limited, and any conventionally known method can be used, except that the textile ink contains polymer A or an emulsion containing polymer A.
• Specific printing methods that can be used include known printing methods such as the inkjet method and the screen method, but the inkjet method is preferred from the standpoints of not requiring plate making, saving resources, saving energy, and facilitating high-resolution expression. In other words, it is preferable to use a method for printing the textile ink of the present invention onto fabric by the inkjet method.
• the printed textile can be produced, for example, by a production method including an image forming step in which the printing ink of the present invention is applied directly to a fabric using an inkjet printer to form an image.
• a transfer printing method using the printing ink of the present invention can also be adopted.
• the production of a printed textile by the transfer printing method includes, for example, a transfer paper production step in which the printing ink of the present invention is discharged onto a transfer paper substrate using an inkjet printer and dried as necessary to produce a transfer paper on which an image has been formed, a transfer step in which the transfer paper produced by the transfer paper production step is superimposed on a fabric and the image formed on the transfer paper is transferred to the fabric by heating and/or pressing, and a peeling step in which the transfer paper is peeled off from the fabric after the image has been transferred by the transfer step.
• the inkjet printer used in the image forming process and transfer paper manufacturing process is not particularly limited, and any conventionally known inkjet printer can be used.
• the inkjet printer may be of any type, such as a piezoelectric type, a thermal type, or a charge change control type (continuous ejection type), and a piezoelectric type inkjet printer is particularly preferred.
• a piezoelectric type inkjet printer there are no particular limitations on the ink ejection conditions. These may be appropriately selected depending on the properties of the ink of the present invention, the type of fabric, the type of image to be printed, and the like.
• the viscosity of the textile printing ink is preferably in the range of 2 to 20 mPa/s, and more preferably in the range of 2 to 10 mPa/s.
• the ink surface tension is preferably in the range of 25 to 45 mN/m.
• the textile printing ink of the present invention is ejected from the nozzle openings of the inkjet printer head and adheres to the fabric surface and the transfer paper substrate, respectively, to form an image.
• the fabric on which the image is formed in the image formation process it is preferable to further heat the fabric on which the image is formed in the image formation process at a temperature above room temperature.
• Heat treatment at a temperature above room temperature can promote the removal of volatile components such as ink-derived solvents contained in the image formed on the fabric, and can promote fixation of the image.
• the adhesion of the image can be improved by the formation of a film (fusion) of the binder resin (polymer A) contained in the ink.
• the heating may be performed simultaneously with the image formation process or the transfer process, or after the image formation process or the transfer process.
• a method of performing heating simultaneously with the image formation process or the transfer process includes a method of performing the image formation process or the transfer process while heating the fabric.
• preferred examples include a heating method using a heating and drying oven, a heating method using a heat press, a heating method using an infrared lamp, and a method using steam such as normal pressure steam or high pressure steam.
• the heating method is preferably performed after the image formation process or the transfer process, since there is a risk of disturbing the air flow if the heating is performed simultaneously.
• the heating temperature is preferably 90 to 180°C.
• the upper limit is more preferably 150°C or less, even more preferably 130°C or less, and particularly preferably 120°C or less, and the lower limit is more preferably 95°C or more, and even more preferably 100°C or more. That is, the heating temperature is preferably 90 to 180°C, more preferably 95 to 150°C, even more preferably 100 to 130°C, and even more preferably 100 to 120°C.
• the heating temperature is not limited to the above range, and may be, for example, a temperature near room temperature, for example, 15 to 25°C.
• the printed material obtained after the above heating may be washed with water and dried.
• ⁇ Average particle size of emulsion particles The average particle size (volume basis) of the emulsion particles was measured using the emulsion obtained in each production example as a measurement sample with a particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000) by dynamic light scattering, and was determined by cumulant method analysis.
• a particle size distribution measuring device manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000
• ⁇ Average particle size of pigment The average particle size (volume basis) of the pigment was measured using the pigment dispersion obtained in each Production Example as a measurement sample with a particle size distribution measuring instrument (manufactured by Otsuka Electronics Co., Ltd., product number: FPAR-1000) based on a dynamic light scattering method, and was determined by cumulant method analysis.
• the ink viscosity was determined by measuring the ink obtained in each of the Examples and Comparative Examples as a measurement sample using an E-type viscometer TPE-100 (manufactured by Toki Sangyo Co., Ltd.) at rotor R24, 0.8 degrees, and 25°C.
• ADEKA REASORB SR-10 a 25% aqueous solution of an emulsifier (manufactured by ADEKA Corporation, trade name: ADEKA REASORB SR-10), and 25 parts of acrylic acid, 565 parts of 2-octyl acrylate, 50 parts of cyclohexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate and 350 parts of methyl methacrylate were prepared as monomer components, of which 44 parts, which corresponds to 3% of the total amount of the pre-emulsion, was added to the flask, and the temperature was raised to 80° C.
• an emulsifier manufactured by ADEKA Corporation, trade name: ADEKA REASORB SR-10
• the resulting reaction liquid was cooled to room temperature and then filtered through a 300-mesh wire screen to obtain emulsion (1) in which emulsion particles (1) containing a polymer having structural units derived from the monomer components used were dispersed.
• the Tg of the resulting emulsion particles (1) was -1°C, and the average particle size of the emulsion particles (1) in emulsion (1) was 200 nm.
• Emulsions (2) to (11) in which emulsion particles (2) to (11) were dispersed were obtained in the same manner as in Polymer Production Example 1, except that the monomer components shown in Table 1 were used.
• the Tg and average particle size of each of the obtained emulsion particles are shown in Table 1.
• the "proportion of monomer b” refers to the mass proportion of monomer b relative to the total monomer components used in the production of the emulsion particles (polymer), that is, it corresponds to the amount of constituent units derived from monomer b in the polymer.
• Pigment Blue 15:3 (LIONOL BLUE FG-7330; manufactured by Toyo Ink Co., Ltd.), 0.1 parts of surfactant Olfin D-10PG (manufactured by Nissin Chemical Industry Co., Ltd.), and zirconia beads with a particle size of 0.5 mm were filled at a volume ratio of 50%, dispersed using a bead mill, and filtered with a pore size filter of 1 ⁇ m (manufactured by Advantec, MCP-1-C10S) to obtain a blue pigment dispersion (pigment dispersion (1)) with a pigment content of 15%.
• the average particle size of the pigment was 90 nm.
• Pigment Dispersion Production Example 2 A mixture of 5 parts of a dispersant, Discoat N-14 (manufactured by Daiichi Kogyo Seiyaku), 6 parts of propylene glycol, 70 parts of deionized water, 100 parts of titanium oxide, CR-95 (manufactured by Ishihara Sangyo Kaisha), and zirconia beads with a particle size of 0.5 mm was filled to 50% by volume and dispersed using a beads mill to obtain a white pigment dispersion (pigment dispersion (2)) with a pigment content of 55%. The average particle size of the pigment was 330 nm.
• Example 1 (Ink manufacturing) 30 parts of emulsion (1) obtained in Polymer Production Example 1 (15 parts as emulsion particles), 23 parts of pigment dispersion (1) obtained in Pigment Dispersion Production Example 1 (3.5 parts as pigment), 2 parts of diethylene glycol monobutyl ether, 15 parts of propylene glycol (moisturizing component), 0.3 parts of surfactant KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 29.7 parts of deionized water were mixed and filtered through a 1 ⁇ m pore size filter (manufactured by Advantec, MCP-1-C10S) to produce ink (1).
• the viscosity of the produced ink (1) was 4 mPa ⁇ s and it was ejectable by inkjet.
• the ink (1) obtained above was introduced into a textile printer MMP-TX13 manufactured by Mastermind, and a solid print of 120 mm x 120 mm was performed on a white cotton fabric (a 100% cotton white T-shirt manufactured by Hanes) at 1440 dpi x 1440 dpi, a print speed setting of 8, and an image was formed on the fabric.
• the fabric on which the image was formed was subjected to a heat treatment for 90 seconds in a hot air dryer at 110°C, to obtain a fabric (1) on which an image was printed.
• the fabric (1) on which the image was printed easily bent and had the same softness as the fabric itself before the image was printed.
• Example 2 to 13 and Comparative Examples 1 to 2 Inks (2) to (13) according to Examples 2 to 13 and inks (C1) to (C2) according to Comparative Examples 1 and 2 were produced in the same manner as in Example 1, except that the type and amount of each component listed in Table 2 were changed as shown in Table 2 and the amount of deionized water added was adjusted so that the total amount was 100 parts.
• the crosslinking agent listed in Table 2 was EPOCROS WS-700 (manufactured by Nippon Shokubai Co., Ltd., solids content 25%).
• the viscosities of the prepared inks (2) to (13) and inks (C1) to (C2) were all 4 to 5 mPa ⁇ s and could be ejected by inkjet.
• Example 1 image formation by the inkjet method and heat treatment were performed in the same manner as in Example 1 to obtain fabrics (2) to (13) and fabrics (C1) to (C2) printed with each image. All of the fabrics printed with images obtained in each Example and Comparative Example were easily bendable and had the same softness as the fabric itself before the image was printed.
• a white cotton fabric a 100% cotton white T-shirt manufactured by Hanes
• a black cotton fabric a 100% cotton black T-shirt manufactured by Hanes
• PG stands for propylene glycol
• TEG stands for triethylene glycol
• the ink of the present invention is suitable for use as a textile printing ink because the resulting printed textile has excellent wet friction fastness.

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• 2023
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