JP2018165336A - Textile ink, textile printing method and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a textile ink that gives a printed matter having excellent color development and washing resistance.SOLUTION: A textile ink contains (A) a colorant, (B) a diene polymer, (C) a light stabilizer, and (D) a liquid medium. When the content of the (B) diene polymer is Mb and the content of the (C) light stabilizer is Mc in the composition, the ratio Mc/Mb is 0.001-1.SELECTED DRAWING: None

Description

  The present invention relates to a textile ink, a textile printing method, and a printed product.

  Inkjet textile printing is a method of dyeing the fabric by discharging ink droplets onto various fabrics (textiles) using an inkjet printer.

  Textile inks used for ink jet textile printing contain dyes that are water-soluble compounds, pigments that are insoluble particles, and the like as pigment components. When inkjet printing is performed using textile inks containing dyes, the textile ink droplets are ejected onto the fabric, and then the dye that has not penetrated the fabric is subjected to washing treatment such as steam treatment, water washing treatment, soaping treatment, etc. It is common to remove and suppress discoloration. However, the printed fabric has a tendency to cause color fading gradually as the dye is gradually eluted by repeated washing.

  When ink-jet printing is performed using a textile-containing ink containing a pigment, the color fading suppression property (hereinafter also referred to as “washing resistance”) during washing is excellent without performing a washing process after printing. However, the pigment has a large particle size, and only the particle surface mainly contributes to the color developability, and the inside of the particle does not greatly contribute to the color developability. Therefore, the color development efficiency per unit volume tends to be low. Therefore, textile inks containing pigments do not have sufficient color developability after printing.

  In order to solve the above-mentioned problem, a method of performing microwave irradiation after ejecting a droplet of textile ink containing a dye and a compound such as urea onto a fabric has been proposed (for example, see Patent Document 1). . In addition, in order to improve the weather resistance of the ink composition, it has been proposed to use a polymer having ultraviolet absorbing ability (see, for example, Patent Document 2).

JP 2010-84289 A Japanese Patent No. 4168477

However, such an ink-jet textile printing method is not always easy because it requires new equipment such as a microwave irradiation device. Further, when the polymer has an ultraviolet absorbing ability, further color development has been demanded. The present invention has been made on the basis of the circumstances as described above, and an object of the present invention is to use ink which can easily perform ink-jet printing and has excellent color developability and washing resistance after printing. It is an object of the present invention to provide a textile printing method, a textile obtained by this textile printing method, and a textile ink agent used for the ink.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the textile ink according to the present invention is:
(A) a coloring material, (B) a diene polymer, (C) a light stabilizer, and (D) a liquid medium,
The ratio Mc / Mb is 0.01 to 10 when the content of the (B) diene polymer in the composition is Mb and the content of the (C) light stabilizer is Mc. To do.

[Application Example 2]
In the textile ink of Application Example 1,
The (B) diene polymer is
A repeating unit (a1) derived from a conjugated diene compound;
A repeating unit (a2) derived from an aromatic vinyl compound;
A repeating unit (a3) derived from an unsaturated carboxylic acid;
Can be contained.

[Application Example 3]
In the textile ink of Application Example 1 or Application Example 2,
The (B) diene polymer may be a particle.

[Application Example 4]
In the textile ink of Application Example 3,
The diene polymer particles may have an average particle size of 50 to 400 nm.

[Application Example 5]
In the textile ink of any one of Application Examples 1 to 4,
The (C) light stabilizer may be a hindered amine light stabilizer.

[Application Example 6]
In the textile ink of any one of Application Examples 1 to 5,
The (D) liquid medium may be water.

[Application Example 7]
It can be a woven fabric using the textile ink of any one of Application Examples 1 to 6.

[Application Example 8]
Discharging the textile ink droplets of any one of Application Examples 1 to 6 and attaching the droplets to the fabric;
A step of heating the fabric after discharging,
And an inkjet textile printing method.

[Application Example 9]
The inkjet textile printing method of application example 8 can include a step of pretreating the fabric.

[Application Example 10]
It can be a textile printed by the inkjet printing method of Application Example 8 or Application Example 9.

  According to the ink of the present invention, a woven fabric can be printed easily, and the color development after printing and the washing resistance are excellent. Especially, it can use suitably for inkjet textile printing. According to the printing method and printed matter of the present invention, it is possible to easily provide a printed matter having excellent color development and washing resistance.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited to only the embodiments described below, and includes various modifications that are implemented without departing from the scope of the present invention. In this specification, “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”. Further, “˜ (meth) acrylic acid ester” is a concept encompassing both “˜acrylic acid ester” and “˜methacrylic acid ester”.
1. Textile Ink The textile ink according to this embodiment contains (A) a color material, (B) a diene polymer, (C) a light stabilizer, and (D) a liquid medium. The textile ink can be suitably used for textile applications, and can be particularly suitably used for inkjet textile printing. Hereinafter, each component contained in the textile ink according to the present embodiment will be described in detail.
1.1. (A) Coloring material The textile ink according to the present embodiment contains (A) a coloring material. The coloring material may be either a dye or a pigment, but a pigment is particularly preferable.
Various dyes such as oil-soluble dyes, direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, and vat dyes can be used as the dye.
As the pigment, inorganic pigments and organic pigments can be used. As the inorganic pigment, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method can be used. Organic pigments include azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindico pigments, isoindolinone pigments, quinofullerone pigments, nitro pigments, and nitiloso pigments. can do.
As the pigment, pigments such as cyan, magenta, yellow, black, and white can be used.
For cyan, for example, C.I. I. Pigment Blue 1, 2, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 56, 60, 63 and the like.
For magenta ink, for example, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 2 (Permanent Red 2B (Ba)), 48: 2 (Permanent Red 2B (Ca)), 48 : 3 (Permanent Red 2B (Sr)), 48: 4 (Permanent Red 2B (Mn)), 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G Lake), 83, 88, 92, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, 2 9, and the like.
For yellow ink, for example, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 150, 153, 155 and the like.
Examples of the black material include carbon black produced by a known production method such as a channel method, an oil furnace method, a furnace method, an acetylene black method, or a thermal black method.
Examples of white mainly include inorganic pigments such as titanium oxide, silicon oxide, zinc oxide, and barium sulfate. Particularly preferred is titanium oxide. Those that have been surface-treated with a hydroxide, oxide, phosphate, or the like of a metal element such as Al, Si, or Zr are preferred.
Examples of intermediate colors include C.I. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 43, C.I. I. Pigment violet 3, 19, 23, 37, C.I. I. Pigment green 7, 36, and the like.

  The color materials exemplified above may be used alone or in combination of two or more. The lower limit of the color material content in the ink is preferably 0.1% by mass, more preferably 0.5% by mass, and even more preferably 1% by mass. On the other hand, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass, further preferably 30% by mass, and particularly preferably 15% by mass. By setting the content of the coloring material in the above range, a high image density can be obtained, the image quality can be improved, better fixing properties and ejection stability can be obtained, and clogging can be suppressed. The viscosity of the ink can be adjusted to an appropriate level.

1.2. (B) Diene Polymer The textile ink according to the present embodiment contains (B) a diene polymer. (B) The diene polymer includes a repeating unit (a1) derived from a conjugated diene compound, a repeating unit (a2) derived from an aromatic vinyl compound, a repeating unit (a3) derived from an unsaturated carboxylic acid, It is preferable to contain. (B) Although a diene polymer is not specifically limited, It is preferable that it is a particulate form. Further, it is preferably a latex in which the (B) diene polymer is dispersed in a liquid medium. It is preferable that the textile ink according to the present embodiment is in the form of a latex because the dispersibility of the coloring material is improved and the coating property is improved in a liquid medium, particularly in an aqueous system.

(B) The diene polymer may be prepared by appropriately adjusting the monomer polymerization method. Hereinafter, each component which may be included in the (B) diene polymer according to the present embodiment will be described.
1.2.1. Repeating units derived from conjugated diene compounds (a1)
(B) The diene polymer contains a repeating unit (a1) derived from a conjugated diene compound. When the repeating unit (a1) derived from the conjugated diene compound is contained, it is preferable because appropriate flexibility can be imparted to the printed ink and the binding property between the colorant and the fabric becomes good.
Although it does not specifically limit as a conjugated diene compound, Specifically, 1, 3- butadiene, 2-methyl- 1, 3- butadiene, 2, 3- dimethyl- 1, 3- butadiene, 2-chloro- 1, 3- Butadiene can be used, and one or more selected from these can be used. Among these, 1,3-butadiene is particularly preferable.

(B) In a diene polymer, when a repeating unit (a1) is included, it is preferable that a content rate is 5-50 mass parts when the sum total of all the repeating units is 100 mass parts, and 10-30 masses. More preferably, it is a part. (B) When the content ratio of the repeating unit (a1) in the diene polymer is in the above range, the printed ink can be provided with appropriate flexibility, and the binding property between the colorant and the fabric can be further increased. Improvement is possible.
1.2.2. Repeating units derived from aromatic vinyl compounds (a2)
(B) The diene polymer contains a repeating unit (a2) derived from a conjugated diene compound. When the repeating unit (a1) derived from the conjugated diene compound is contained, it is preferable because appropriate flexibility can be imparted to the printed ink and the binding property between the coloring materials becomes good.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, and the like, and can be one or more selected from these. Among the above, the aromatic vinyl compound is particularly preferably styrene.
(B) In the diene polymer, the content of the repeating unit (a2) derived from the aromatic vinyl compound is preferably 10 to 40 parts by mass when the total of all the repeating units is 100 parts by mass. It is more preferable that it is 15-35 mass parts. When the content ratio of the repeating unit (a2) is within the above range, it is preferable because appropriate flexibility can be imparted to the printed ink and the binding property between the coloring materials becomes good.
1.2.3. Repeating unit derived from unsaturated carboxylic acid (a3)
(B) The polymer may contain a repeating unit (a3) derived from an unsaturated carboxylic acid. The use of the repeating unit (a3) derived from an unsaturated carboxylic acid is preferable because the dispersibility of the coloring material can be improved in a liquid medium, particularly in an aqueous system, when the textile ink is latex.
Although it does not specifically limit as unsaturated carboxylic acid, Specifically, monocarboxylic acid or dicarboxylic acid, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, can be mentioned, and it selects from these One or more of the above can be used. As the unsaturated carboxylic acid, it is preferable to use one or more selected from acrylic acid and methacrylic acid.

(B) In a diene polymer, when a repeating unit (a3) is included, it is preferable that a content rate is 1-99 mass parts when the sum total of all the repeating units is 100 mass parts, 10-90 masses More preferably, it is a part. (B) When the content rate of the repeating unit (a3) in a diene polymer exists in the said range, since the dispersibility of a coloring material can be improved, it is preferable.
1.2.4. Other repeating units (a4)
(B) The diene polymer may have a repeating unit other than the above. Examples of the repeating unit other than the above (a4) include a repeating unit derived from an unsaturated carboxylic acid ester, a repeating unit having a nitrile group, and an aromatic polyfunctional vinyl compound.
As the repeating unit derived from the unsaturated carboxylic acid ester, a (meth) acrylic acid ester can be preferably used. Specific examples of (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) acrylic acid. n-butyl, i-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene di (meth) acrylate Glycol, propylene glycol di (meth) acrylate, trimethylol propylene tri (meth) acrylate , Tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate dipentaerythritol can be mentioned (meth) allyl acrylate, can be at least one selected from among these.
Examples of the repeating unit having a nitrile group include an α, β-unsaturated nitrile compound. Specific examples of the α, β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, and the like. Can be. Among these, the aromatic polyfunctional vinyl compound is preferably one or more selected from acrylonitrile and methacrylonitrile, and more preferably acrylonitrile, for example, aromatics such as divinylbenzene and diisopropenylbenzene. Although a divinyl compound is mentioned, it is not restricted to these. Of these, divinylbenzene is preferred. The aromatic polyfunctional vinyl compounds exemplified above may be used alone or in combination of two or more.

(B) When the diene polymer contains an aromatic polyfunctional vinyl compound, the content is preferably 0.1 to 50 parts by mass when the total of all repeating units is 100 parts by mass. More preferably, it is -20 mass parts. (B) When the content ratio of the repeating unit in the diene polymer is within the above range, the binding property can be further improved.
The (B) diene polymer particles may further have a repeating unit derived from the compound shown below. Examples of such compounds include fluorine-containing compounds having an ethylenically unsaturated bond such as vinylidene fluoride, ethylene tetrafluoride and propylene hexafluoride, and ethylenically unsaturated carboxylic acids such as (meth) acrylamide and N-methylolacrylamide. Acid alkyl amides, vinyl acetates such as vinyl acetate and vinyl propionate, acid anhydrides of ethylenically unsaturated dicarboxylic acids, monoalkyl esters, monoamides, aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide Aminoalkylamides of ethylenically unsaturated carboxylic acids such as vinyl sulfonic acid, styrene sulfonic acid, allyl sulfonic acid, sulfoethyl methacrylate, sulfopropyl methacrylate, sulfobutyl methacrylate Examples include compounds having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxy-3-acrylamidopropanesulfonic acid, and 3-allyloxy-2-hydroxypropanesulfonic acid. It can be one or more selected from.
1.2.5. Molecular weight regulator (a5)
Examples of the molecular weight modifier (a5) include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethylxanthogen disulfide, diisopropylxanthogen Xanthogen compounds such as disulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetramethylthiuram monosulfide; phenol compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol Allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane and carbon tetrabromide; α-benzyl In addition to vinyl ether compounds such as xylstyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, etc., triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α- Examples thereof include, but are not limited to, methylstyrene dimer. Of these, dodecyl mercaptan is preferred. The above exemplified molecular weight regulators may be used alone or in combination of two or more.

(B) In a polymer, when a molecular weight modifier (a5) is included, it is preferable that a content rate is 0.1-50 mass parts when the sum total of all the repeating units is 100 mass parts, 1-20 More preferably, it is part by mass. (B) When the content ratio of the molecular weight modifier (a5) in the diene polymer is within the above range, the binding property can be further improved.
The lower limit of the diene polymer content in the ink is preferably 0.5% by mass, and more preferably 1.0% by mass. On the other hand, the upper limit of the content of the diene polymer is preferably 20% by mass, more preferably 10% by mass, and still more preferably 8% by mass. By setting the content of the diene polymer in the above range, the textile ink can be easily fixed with fibers.

1.2.6. (B) Number average particle diameter of diene polymer (B) When the diene polymer is a particle, the number average particle diameter of the diene polymer particle is preferably in the range of 20 to 450 nm, 30 to It is more preferably in the range of 420 nm, particularly preferably in the range of 50 to 400 nm.

  It is preferable that the number average particle diameter of the diene polymer particles is in the above range because the stability of the textile ink is improved, the dispersibility of the coloring material is improved, and the coating property is also improved.

  The number average particle size of the diene polymer particles is a particle size distribution measuring apparatus using a light scattering method as a measurement principle, and the cumulative frequency of the number of particles when the particles are accumulated from small particles is 50. % Particle diameter (D50). Examples of such a particle size distribution measuring apparatus include Coulter LS230, LS100, LS13320 (above, manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and the like. These particle size distribution measuring devices are not intended to evaluate only the primary particles of the polymer particles, but can also evaluate the secondary particles formed by aggregation of the primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an indicator of the dispersion state of the polymer particles contained in the composition.

1.2.7. (B) Molecular weight of diene polymer (B) Polymerization average molecular weight (Mw) of diene polymer is preferably 10,000 or more, more preferably 100,000 or more, and particularly preferably 5,000,000 or more. (B) It is preferable for the molecular weight of the diene polymer to be in the above-mentioned range since the dispersibility of the coloring material is improved and the coating property is also improved.

1.2.8. (B) Endothermic property of diene polymer (B) The diene polymer has an endothermic peak in a temperature range of −50 to + 80 ° C. when differential scanning calorimetry (DSC) is performed according to JIS K7121. Preferably only one is observed. (B) The endothermic behavior of the diene polymer is presumed to correlate with the shape stability of the polymer particles. For this reason, if the endothermic peak of the (B) diene polymer is within the above temperature range, it can be presumed that the shape stability of the polymer is good and the ink when printed can have sufficient strength. .

1.2.9. (B) Production method of diene polymer (B) When the diene polymer is a diene polymer particle, it may be produced by one-stage polymerization, two-stage polymerization, or further by multi-stage polymerization, Each polymerization can be carried out in the presence of a known polymerization initiator, molecular weight regulator, emulsifier (surfactant) and the like.

1.3. (C) Light Stabilizer The textile ink according to this embodiment further contains (C) a light stabilizer. (C) Examples of light stabilizers include hindered phenol antioxidants, hindered phenol ultraviolet absorbers, organic sulfur antioxidants, organic phosphorus antioxidants, hindered amine light stabilizers, and benzotriazole ultraviolet rays. Examples include absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, organic nickel-based UV absorbers, and triazine-based UV absorbers. Among these, a hindered amine light stabilizer is particularly preferable. Moreover, the light stabilizer illustrated above may be used alone or in combination of two or more. Moreover, in this specification, (C) light stabilizer shall not contain (A) color material.

  Examples of hindered phenol antioxidants include 2,6-di-tert-butyl-4-phenylmethyl-phenol, 2,6-di-tert-butyl-4-phenylphenol, and 2,6-di-tert. -Butyl-P-cresol, 4,4'-thiobis- (6-tert-butyl-3-methylphenol), 4,4'-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2 '-Methylenebis- (4-methyl-6-tert-butylphenol), 2,2'-methylenebis- (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-ethylphenol, 1,1,3-tris (2-methyl-4hydroxy-5-tert-butylphenyl) butane, n-octadecyl-3- (3,5-di-t rt-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, triethyleneglycolbis [3- (3-tert-butyl -4-hydroxy-5-methylphenyl) propionate], tris (3,5-di-tert-butyl-4 · hydroxybenzyl) isocyanurate, triethylene glycol-bis [3- (3-t-butyl-5 -Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n- Octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5- Liazine, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Adekastab AO-50 (manufactured by ADEKA)), N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxy) Ethyl benzylphosphonate) calcium, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, octylated diphenylamine, 2,4, -bis [(octylthio) methyl] -O-cresol , Isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4-thiobis- (2-tert-butyl-5-methylphenol), pentaerythritol tetrakis- (3,5 -Di-t-butyl-4-hydroxyhydrocinnamate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) (Adeka Stub AO-20 (manufactured by ADEKA)), 1,3,5-tris (4-t-butyl-3-hydroxy- , 6-Dimethylbenzyl) isocyanuric acid butylated hydroxyanisole, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, bis [3,3′-bis (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, tocopherols, and the like.

  Examples of the hindered phenol ultraviolet absorber include 2 ', 4'-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

  Examples of the organic sulfur-based antioxidant include specific compounds of the organic sulfur-based antioxidant, such as dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate. , Pentaerythritol tetrakis- (3-dodecylthiopropionate), and the like.

  Examples of the organic phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, And tri (2,4-dibutylphenoxy) phosphine.

  Specific examples of the hindered amine light stabilizer include, for example, bis- [2,2,6,6-tetramethyl-4-piperidinyl] sebacate (Sanol LS-770 (manufactured by Sankyo), Adekastab LA-77 (ADEKA) )), Bis- [N-methyl-2,2,6,6-tetramethyl-4-piperidinyl] sebacate (TINUVIN 765 (manufactured by BASF), SANOL LS 765 (manufactured by Sankyo)), bis- (1 , 2,2,6,6-pentamethyl-4-piperidinyl) -2- (3,5-di-tetra-butyl-4-hydroxybenzyl) -2-n-butyl malonate (TINUVIN 144 (manufactured by BASF)) ), Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate (a) Castab LA-57 (manufactured by ADEKA)), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate (Adekastab LA-52 (ADEKA) Manufactured))), 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate (Adekastab LA-67 (manufactured by ADEKA), 1,2,2 , 6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butane tetracarboxylate (Adekastab LA-62 (manufactured by ADEKA)).

Specific examples of the benzotriazole ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl. ] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2 -(2'-hydroxy-5'-t-octylphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzoto) Azol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivative, 5-chloro-2- (3,5-di-t-butyl-2 -Hydroxyphenyl) -2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl) -2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (2H-benzotriazol-2-yl) -4 -Methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-4- Octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-octylphenyl) -benzotriazole and the like. .
Specific examples of the benzophenone ultraviolet absorber include 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, and 2-hydroxy-4- Octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′- And dimethoxybenzophenone, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, and the like.

Specific examples of salicylate ultraviolet absorbers include phenyl salicylate and 4-t-butylphenyl salicylate.
Specific examples of the cyanoacrylate ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like.
Specific examples of the organic nickel-based UV absorber include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), 2,2-thiobis (4-t -Octylphenolate) -n-butylamine nickel (II), and the like.
As a specific compound of the triazine-based ultraviolet absorber, for example, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) pheno -Le, etc. You may use the said organic solvent individually or in combination of 2 or more types.
The lower limit of the content of the light stabilizer in the ink is preferably 0.01% by mass, and more preferably 0.1% by mass. On the other hand, as an upper limit of content of the said light stabilizer, 10 mass% is preferable and 8 mass% is more preferable. By making content of the said light stabilizer into the said range, the said textile ink can be made easy to fix with a fiber.
In the textile ink according to the present embodiment, when the content of the (B) diene polymer in the ink is Mb mass part and the content of the (C) light stabilizer is Mc mass part, Mc / Mb = It is preferably in the range of 0.001-1, more preferably in the range of 0.05-0.8, and still more preferably in the range of 0.01-0.8. When Mc / Mb is in the above range, the (B) diene polymer and the (C) light stabilizer are appropriately mixed with each other, and are dispersed by surrounding the color material after printing. The inventor presumes that the outline of the printed material is less likely to bleed and exhibits further color development.

1.4. (D) Liquid medium The textile ink according to this embodiment further contains (D) a liquid medium. (D) Although it does not specifically limit as a liquid medium, For example, the mixed solvent containing water, water, and an organic solvent etc. are mentioned. An aqueous medium containing water is preferred.

  The aqueous medium is not particularly limited, but pure water is preferable. This pure water can be produced, for example, by ion exchange or distillation. The pure water is preferably sterilized with ultraviolet rays or the like.

  Although it does not specifically limit as an organic solvent, From a viewpoint of adjusting a viscosity to a moderate thing and a viewpoint of odor suppression, an alcohol is preferable and the alcohol whose boiling point in 1 atmosphere is 150 degreeC or more is more preferable. Examples of such an alcohol include keto alcohol having a boiling point of 150 ° C. or higher at 1 atm and a polyhydric alcohol having a boiling point of 150 ° C. or higher at 1 atm.

  Examples of the keto alcohol having a boiling point at 1 atm of 150 ° C. or higher that can be used for the ink include diacetone alcohol.

  Examples of the polyhydric alcohol having a boiling point of 150 ° C. or higher that can be used in the ink include ethylene glycol polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol, glycerin, propylene glycol, Dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2,000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-pentane Diol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,8-octanediol, 1,2-octanediol, Seo erythritol, pentaerythritol, and 2-mercaptoethanol. As said polyhydric alcohol, ethylene glycol type polyhydric alcohol and glycerol are preferable, and diethylene glycol and glycerol are more preferable.

  As said liquid medium, the mixed solvent containing water and an organic solvent is preferable, The mixed solvent containing water, keto alcohol, and a polyhydric alcohol is more preferable, The mixed solvent containing water, diacetone alcohol, diethylene glycol, and glycerol is further more preferable.

When the ink contains a liquid medium, the lower limit of the content of the liquid medium in the ink is preferably 10% by mass, more preferably 20% by mass, and even more preferably 50% by mass. On the other hand, the upper limit of the content of the liquid medium is preferably 95% by mass, and more preferably 80% by mass. By setting the content of the liquid medium in the above range, the viscosity of the ink can be adjusted to a more appropriate level.
When the ink contains water, the lower limit of the water content in the ink is not particularly limited, but is preferably 5% by mass and more preferably 10% by mass. On the other hand, the upper limit of the water content is not particularly limited, but is preferably 90% by mass, more preferably 85% by mass, further preferably 80% by mass, particularly preferably 70% by mass, and most preferably 50% by mass. . By setting the water content in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

  When the ink contains keto alcohol, the lower limit of the keto alcohol content in the ink is not particularly limited, but is preferably 5% by mass and more preferably 20% by mass. On the other hand, the upper limit of the keto alcohol content is not particularly limited, but is preferably 80% by mass, and more preferably 60% by mass. By setting the keto alcohol content in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

  When the ink contains a polyhydric alcohol, the lower limit of the polyhydric alcohol content in the ink is not particularly limited, but is preferably 1% by mass and more preferably 5% by mass. On the other hand, the upper limit of the content of the polyhydric alcohol is not particularly limited, but is preferably 40% by mass, and more preferably 20% by mass. By setting the content of the polyhydric alcohol in the above range, the viscosity of the ink can be adjusted to a more appropriate level.

  The textile ink according to the present embodiment uses (D) an aqueous medium as a liquid medium, and preferably contains no non-aqueous medium other than water, so that it has a low adverse effect on the environment and is safe for handling workers. Increases the nature.

1.5. Other Components The textile ink according to this embodiment may further contain other additives in addition to the components described above. Examples of the other additives include hydrotropic agents, alkylene glycol monoalkyl ethers, surfactants, preservatives, chelating agents, etc. The hydrotropic agent used in the ink breaks hydrogen bonds in the liquid medium. By doing so, the affinity of the textile ink agent and the liquid medium is improved. Examples of the hydrotropic agent include urea, dimethylurea, thiourea, monomethylthiourea, dimethylthiourea and the like, and urea is preferable.

  When the ink contains a hydrotropic agent, the lower limit of the hydrotropic agent content in the ink is preferably 1% by mass and more preferably 5% by mass. On the other hand, the upper limit of the content is preferably 40% by mass, and more preferably 25% by mass. By setting the content in the above range, the affinity of the textile ink agent and the liquid medium can be further improved.

  The alkylene glycol monoalkyl ether and the surfactant improve the stability when the ink is ejected by an ink jet printer, in particular, the stability when ejected by an ink jet printer using a piezo head. Examples of the alkylene glycol monoalkyl ether include triethylene glycol mono-n-butyl ether. Examples of the surfactant include acetylene glycol surfactants. The upper limit of each content of the alkylene glycol monoalkyl ether and the surfactant in the ink is not particularly limited, but is 20% by mass, for example.

  Examples of the preservative used in the ink include “Proxel CRL”, “Proxel BDN”, “Proxel GXL”, “Proxel XL2”, “Proxel IB”, and “Proxel TN” manufactured by Avecia.

  When the ink contains a preservative, the lower limit of the content of the preservative in the ink is preferably 0.01% by mass, more preferably 0.1% by mass, and even more preferably 0.5% by mass. On the other hand, the upper limit of the content of the preservative is preferably 1% by mass, more preferably 0.2% by mass, and still more preferably 0.5% by mass. By making content of the said preservative into the said range, antiseptic property can fully be exhibited, without reducing color developability etc.

  The chelating agent used in the ink improves the reliability of the ink by trapping the metal in the ink, and prevents dyeing spots by trapping the heavy metal of the fabric. As the chelating agent, ethylenediaminetetraacetate, nitrilotriacetate, hexametaphosphate, pyrophosphate and metaphosphate are preferable. Moreover, as a commercial item of the said chelating agent, "TRILON TA" and "DEKOL SN" of BASF, and "Calgon T" of Benkiesed are preferable. Since the commercial products of these chelating agents are excellent in biodegradability, the environmental load can be reduced. The upper limit of the content of the chelating agent in the ink is not particularly limited, but is, for example, 5% by mass.

1.6. Ink Production Method The ink production method is not particularly limited, and can be obtained by mixing the above-described components by a conventionally known method.
2. Textile printing method Next, a textile printing method using the ink will be described. This textile printing method includes a step of discharging ink droplets and attaching the droplets to the fabric (discharge step), and a step of heating the fabric after the discharge step (heating step). The textile printing method may further include a step (pretreatment step) of pretreating the fabric before the discharging step. Since the textile printing method uses the ink, the washing process after the ejection process can be omitted, and the printed matter obtained is excellent in color developability and washing resistance.

  The woven fabric used in the above printing method is not particularly limited. For example, it is formed of fibers such as natural fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyester, nylon and polyurethane, and semi-synthetic fibers such as acetate fibers. Woven fabrics.

[Pretreatment process]
In this step, the textile is pretreated before the discharging step in order to improve the fixing property of the textile ink agent contained in the ink to the textile. Examples of the pretreatment method include a method of applying a pretreatment agent to the woven fabric.

  As said pretreatment agent, what contains a hydrotropic agent, aqueous metal salt, a pH adjuster, a pH buffer, an aqueous polymer etc. can be used, for example. The pretreatment agent may further contain additives such as a water repellent and a surfactant.

  Examples of the hydrotropic agent include urea, dimethylurea, thiourea, monomethylthiourea, dimethylthiourea and the like.

  Examples of the aqueous metal salt include alkali metal salts and alkaline earth metal salts.

  Examples of the pH adjusting agent include acid ammonium salts such as ammonium sulfate and ammonium tartrate.

Examples of the aqueous polymer include starch substances such as corn and wheat, cellulosic polymers such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose, polysaccharides such as sodium alginate, arabic gum, locust bean gum, trantogum, guar gum, and tamarind seeds. Natural aqueous polymers such as polymers, protein substances such as gelatin and casein, tannin substances, lignin substances,
Examples thereof include synthetic aqueous polymers such as polyvinyl alcohol, polyethylene oxide, acrylic acid polymers, and maleic anhydride polymers.

[Discharge process]
In this step, the ink droplets are ejected and adhered to the fabric. As a method of discharging the ink droplets, an ink jet method is preferable. The inkjet printer used in the inkjet method is not particularly limited, and a commercially available printer can be used.

[Heating process]
In this step, the fabric after the discharging step is heated to remove volatile components such as a liquid medium in the ink. The heating temperature is, for example, 70 ° C. or higher and 140 ° C. or lower. The heating time is, for example, from 30 seconds to 20 minutes, and preferably from 30 seconds to 5 minutes. By setting the heating temperature and the heating time in the above ranges, the volatile components can be reliably removed while suppressing thermal decomposition of the textile ink agent.
3. EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. “Part” and “%” in Examples and Comparative Examples are based on mass unless otherwise specified.

3.1. Synthesis example 3.1.1. (B) Synthesis of diene polymer (b1) In a temperature-controllable autoclave with a stirrer, 300 parts by mass of ion exchange water, 1.5 parts by mass of sodium dodecylbenzenesulfonate, 0.5 parts by mass of potassium persulfate, Sodium bisulfite 0.1 part, α-methylstyrene dimer 0.1 part, dodecyl mercaptan 0.1 part, acrylonitrile 10 part, acrylic acid 2 part, methacrylic acid 2 part, methyl methacrylate 11 70 parts by mass, 1,3-butadiene 40 parts by mass, and styrene 35 parts by mass, after sufficiently stirring, heated to 45 ° C. for 24 hours, then added 0.5 parts by mass of potassium persulfate 70 The temperature was raised to ° C and the reaction was carried out for 4 hours. The polymerization conversion rate determined from the solid content concentration was about 99%. After cooling to 40 ° C., the pH of the latex is adjusted to 7.5 with sodium hydroxide, the residual monomer and water are evaporated under reduced pressure, and (b1) an aqueous dispersion containing 40% of the polymer is obtained. Produced.
About the aqueous dispersion obtained above, the particle size distribution is measured using a particle size distribution measuring apparatus (model “FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.) having a dynamic light scattering method as a measurement principle, and the particle size distribution is obtained. The number average particle diameter (Da1) was determined from the result of 200 nm.

3.1.2. Synthesis of Polymer (b2) Having Ultraviolet Absorber Dispersed particles of polymer fine particles containing UV absorber 2 (2′-hydroxy-5′-methylphenyl) benzotriazole by the method described in the example of Japanese Patent No. 4168477 A polymer emulsion (b2) was obtained.

3.2. Example 1
Through a known procedure (step), an ink (I-1) having the composition and content described in Table 1 was prepared. In addition, content of (b1) and (b2) in a table | surface represents the mass% of solid content.
Example 1 A droplet of ink (I-1) was ejected onto a pretreated silk white cloth using an ink jet printer, dried at 80 degrees for 5 minutes, and then held in heated steam at 170 degrees for 7 minutes. A printed product was obtained. As the inkjet printer, “TX2-1600” manufactured by Mimaki Engineering Co., Ltd. was used, and the printing density was 100%. In addition, as the pretreatment, the silk white cloth was immersed in a pretreatment agent (guar gum: ammonium sulfate: urea: water = 2: 4: 10: 84) for 1 minute. In addition, “NP8” manufactured by Sansho Co., Ltd. was used as guar gum.
3.3. Examples 2-7 and Comparative Examples 1-4
In Example 1, inks (I-2) to (I-11) were prepared in the same manner as in Example 1 except that the compositions and contents described in Table 1 were used, and the same printing method as in Example 1 was used. The printed matter of Examples 2-7 and Comparative Examples 1-4 was obtained.

3.4. Evaluation The printed matter obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was washed with water, and the fastness to washing was measured. Specifically, the printed matter was stirred in water at 60 ° C. for 60 minutes, and then the printed matter was squeezed and the collected waste water was observed for measurement. In the printed products of Examples 1 to 7, colored wastewater did not come out when washed with water (results were evaluated as ◯), and in particular, Examples 2 to 6 hardly occurred (results were evaluated as ◎). On the other hand, the printed matter of Comparative Examples 1 to 4 produced a large amount of colored wastewater when washed with water (the result is Δ). Note that the printed matter of Comparative Example 2 was not able to be evaluated for color development because almost all of the dye flowed out when washed with water (the result is x). These results are shown in Table 1.

  Next, visual evaluation of color development was performed on the printed matters of Examples 1 to 7 and Comparative Examples 1 to 4 after washing with water. The printed products of Examples 1 to 7 were clean printed products having no blur (results are given as ◯), and Examples 2 to 6 were not particularly blurred (results were given as ◎). Moreover, the printed matter of Examples 1-8 was very excellent in saturation and color intensity (color value). On the other hand, in the printed materials of Comparative Examples 1 to 4, bleeding was confirmed (the result was Δ), and in particular, the bleeding of Comparative Examples 2 to 4 was worse (the result was X). These results are shown in Table 1.

Abbreviations of compounds in Table 1 have the following meanings, respectively. The “-” in the column indicates that the composition was not used or has no value.
C. I. Pigment Yellow 74 (manufactured by Dainichi Seika Kogyo Co., Ltd.)
C. I. Pigment Blue 15: 4 (manufactured by Dainichi Seika Kogyo)
LA-77: ADK STAB LA-77 (manufactured by ADEKA)
TINUVIN 765: TINUVIN 765 (manufactured by BASF)
AO-50: ADK STAB AO-50 (made by ADEKA)
Proxel XL2: Proxel XL2 (Avecia)
As is apparent from the examples, the ink is judged to be excellent in washing resistance after printing and excellent in color development after washing. On the other hand, as can be seen from Comparative Example 1, it can be seen that the effect is superior to the ink using the polymer containing the ultraviolet absorber. Further, as can be seen from Comparative Example 2, it can be seen that the ink containing no light stabilizer or the ink whose Mc / Mb is outside the scope of claims of the present application is inferior in washing resistance and color development.

  The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

Claims (10)

(A) a coloring material, (B) a diene polymer, (C) a light stabilizer, and (D) a liquid medium,
The ratio Mc / Mb when the content of the (B) diene polymer in the composition is Mb and the content of the (C) light stabilizer is Mc is 0.001-1. Textile ink. The (B) diene polymer is
A repeating unit (a1) derived from a conjugated diene compound;
A repeating unit (a2) derived from an aromatic vinyl compound;
A repeating unit (a3) derived from an unsaturated carboxylic acid;
The textile ink according to claim 1, comprising:   The textile ink according to claim 1 or 2, wherein the (B) diene polymer is a particle.   The textile ink according to claim 3, wherein the diene polymer particles have an average particle diameter of 50 to 400 nm.   The textile ink according to any one of claims 1 to 4, wherein the (C) light stabilizer is a hindered amine light stabilizer.   The textile ink according to any one of claims 1 to 5, wherein the liquid medium (D) is water.   A woven fabric using the textile ink according to any one of claims 1 to 6. Discharging the droplets of textile ink according to any one of claims 1 to 6 and attaching the droplets to the fabric;
A step of heating the fabric after discharging,
An inkjet printing method comprising: The inkjet printing method according to claim 8, further comprising a step of pretreating the fabric. A woven fabric printed by the ink-jet printing method according to claim 8 or 9.