JP2017155110A - Printing inkjet ink composition, and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing inkjet ink composition having improved light resistance and washing fastness, and an inkjet recording method.SOLUTION: A printing inkjet ink composition has a resin dispersion, a colorant, and water, and also has at least one of an ultraviolet absorber or a light stabilizer.SELECTED DRAWING: None

Description

  The present invention relates to a textile printing inkjet ink composition and an inkjet recording method.

Conventionally, there has been known an ink jet printing method in which an aqueous pigment ink is printed on a cloth or the like by an ink jet method using an ink jet printer.
For example, Patent Document 1 proposes an ink jet printing method in which a textile fiber product subjected to a specific pretreatment is printed using an aqueous pigment ink to which a reactive blocked isocyanate compound is added.

JP 2014-129617 A

  However, the inkjet printing method described in Patent Document 1 has a problem that fading easily occurs in a colored portion (printed portion) when a printed fabric (cloth-like fiber product) is exposed to sunlight or the like for a long time. there were. For example, water-based pigment inks used for textile printing and the like use different types of pigments having various molecular structures in order to improve color reproducibility. Among these pigments, there is a pigment whose molecular structure is destroyed by ultraviolet rays contained in sunlight and the like, and the original color development cannot be maintained. The strength (light resistance) of the molecular structure with respect to such ultraviolet rays varies depending on the type of pigment. For this reason, the fading of the printing part does not proceed uniformly, but the specific color tends to fade and the color tone tends to change. Therefore, when the water-based pigment ink disclosed in Patent Document 1 is used for printing on curtains and summer clothing, the appearance of the printed portion may be deteriorated due to fading.

  In addition, the printed fabric may lose color due to the color material falling off by washing. This is also a problem for fabrics that are frequently washed, such as summer clothing. There is a need for improved light fastness and improved wash fastness.

  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 forms or application examples.

  [Application Example] The textile printing ink-jet ink composition according to this application example contains a resin dispersion, a coloring material, and water, and further contains at least one of an ultraviolet absorber or a light stabilizer. And

  According to this application example, even when exposed to sunlight or the like for a long time, it is possible to suppress the occurrence of fading in the printed portion. Specifically, a resin dispersion, a coloring material, an ultraviolet absorber, a light stabilizer, and the like coexist in a textile printing ink-jet ink composition (hereinafter also simply referred to as “ink”). When this ink is used to print a fabric by an ink jet method, the resin dispersion in the ink forms a resin film in the vicinity of the fabric surface at the printing portion. This film includes a coloring material and an ultraviolet absorber or a light stabilizer, and prevents them from penetrating into and between the fibers constituting the fabric. Therefore, the coloring material and the ultraviolet absorber or light stabilizer approach each other and remain in the vicinity of the surface of the fabric. When the color material and the ultraviolet absorber or the light stabilizer are present in the vicinity, fading of the color material due to sunlight or the like can be effectively suppressed. Thereby, even if it uses for a curtain or summer clothing, discoloration is suppressed and the appearance of a textile printing part becomes difficult to deteriorate. That is, it is possible to provide a textile printing inkjet ink composition with improved light resistance.

  Further, as described above, since the color material is included in the film formed by the resin dispersion, for example, even if a pigment is used as the color material, the pigment is protected by the above film, and the color caused by the dropping of the pigment during washing Drop is suppressed. Thereby, washing fastness can be improved.

  The textile inkjet ink composition described in the above application example preferably contains an ultraviolet absorber and a light stabilizer.

  According to this, the light resistance of the textile inkjet ink composition can be further improved. Specifically, the ultraviolet absorber has a function of converting light energy into heat energy and suppressing oxidation by light. The light stabilizer has a function of capturing radicals generated by photooxidation and suppressing fading caused by the radicals. Therefore, the combined use of the ultraviolet absorber and the light stabilizer can further suppress the fading of the printed portion.

  In the textile inkjet ink composition described in the above application example, the coloring material is C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 254, C.I. I. Pigment violet 19, C.I. I. It is preferable to include at least one pigment selected from CI Pigment Violet 23.

  According to this, it is possible to select a color material from the hue, saturation, and lightness provided without paying attention to the weakness of light resistance. Thereby, the color reproducibility of a textile printing part can be improved.

  In the textile inkjet ink composition described in the above application example, the coloring material is C.I. I. Pigment green 7, C.I. I. It is preferable that at least one pigment selected from CI Pigment Green 36 is included.

  According to this, it is possible to maintain the appearance of the printed portion by improving the light fastness in a color material in which a change in fading is easily perceived as compared with other colors.

  In the textile inkjet ink composition described in the above application example, it is preferable that at least one of the ultraviolet absorber and the light stabilizer is an aqueous dispersion.

  According to this, since the particles of the ultraviolet absorber and the light stabilizer are dispersed in the ink, sedimentation of the particles is suppressed. Thereby, the uniformity of the ultraviolet absorber and the light stabilizer in the ink is improved, and the light resistance is stabilized by being uniformly distributed in the printed portion. In addition, clogging due to sedimentation of ink storage containers (ink cartridges), ink jet heads, ink paths of ink jet printers, and the like is reduced. Thereby, the ejection stability and reliability of the ink jet printer can be improved.

  In the textile inkjet ink composition described in the above application example, it is preferable that the ultraviolet absorber contains at least one selected from triazine compounds and benzotriazole compounds.

  According to this, since organic ultraviolet absorbers such as triazine compounds and benzotriazole compounds have a wider ultraviolet absorption wavelength range than inorganic ultraviolet absorbers, coloring materials having various molecular structures can be obtained. Light resistance can be improved.

  In the textile inkjet ink composition described in the above application example, the light stabilizer preferably includes a hindered amine compound.

  According to this, it is possible to capture radicals generated by photooxidation and suppress fading caused by radicals. Thereby, the light resistance of the textile printing inkjet ink composition can be improved.

  In the textile inkjet ink composition described in the above application example, the content of the ultraviolet absorber is preferably 0.3% by mass or more and 5.0% by mass or less with respect to the total mass of the ink composition.

  In the textile printing inkjet ink composition described in the above application example, the content ratio of the light stabilizer is preferably 0.3% by mass or more and 5.0% by mass or less with respect to the total mass of the ink composition.

  According to these, the light resistance of the printed part can be improved, and the increase in the viscosity of the ink due to the addition of the ultraviolet absorber or the light stabilizer can be suppressed. By suppressing the increase in the viscosity of the ink, the ejection stability of the ink from the inkjet head can be improved.

  In the textile printing inkjet ink composition described in the above application example, the content ratio of the solid content of the resin dispersion is 2.0% by mass or more and 25.0% by mass or less with respect to the total mass of the ink composition. Is preferred.

  According to this, it is possible to ensure the abrasion resistance of the printed portion and to suppress the increase in the viscosity of the ink. By suppressing the increase in the viscosity of the ink, the ejection stability of the ink from the inkjet head can be improved.

  In the textile inkjet ink composition described in the above application example, it is preferable that the resin dispersion contains a urethane resin.

  According to this, since a resin film containing a urethane resin is formed, the abrasion resistance and flexibility of the printed portion are improved. Specifically, since the urethane-based resin has a hard segment and a soft segment in the basic skeleton, the toughness of the film is improved and the tenacity is imparted. As a result, a resin film resistant to sliding and bending can be formed.

  The inkjet recording method described in this application example is characterized in that recording is performed on a recording medium by the inkjet method using the textile printing inkjet ink composition described in the above application example.

  According to this application example, it is possible to provide an ink jet recording method that improves light resistance of recording of images, text, patterns, colors, and the like on a recording medium. In addition, by applying the textile printing inkjet ink composition as fine droplets using the inkjet method, the recording can be performed with a higher resolution and the appearance can be improved as compared with methods other than the inkjet method.

1 is a schematic perspective view showing an inkjet printing apparatus according to Embodiment 1. FIG.

  The textile printing ink-jet ink composition (ink) is used for printing textiles. The textile printing inkjet ink composition according to this embodiment contains a resin dispersion, a coloring material, and water, and further contains at least one of an ultraviolet absorber or a light stabilizer. Hereinafter, each component contained in the ink according to the present embodiment will be described.

<Color material>
As the color material contained in the ink of the present embodiment, it is preferable to use a dye or a pigment.
Examples of the dye include water-soluble dyes such as acid dyes, and disperse dyes using a dispersant (surfactant) in combination. Known dyes can be used as these dyes. The above dyes require pre-treatment on the fabric and post-treatment after printing. Therefore, in digital textile printing using the ink jet method, it is more preferable to use a pigment that can be easily pretreated or posttreated as a color material.

  As the pigment, any of known organic pigments and inorganic pigments can be used. Examples of organic pigments include azo pigments such as azo lake pigments, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, and isoindolinone pigments. , Isoindoline pigments, quinophthalone pigments, diketopyrrolopyrrole pigments and other polycyclic pigments, basic dye type lakes, acid dye type lakes and other dye lake pigments, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, etc. Is mentioned. Examples of the inorganic pigment include metal oxide pigments such as titanium dioxide, zinc oxide, and chromium oxide, and carbon black.

  Examples of pigments for magenta ink or red ink include C.I. I. (Colour Index Generic Name) Pigment 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 254, C.I. I. Pigment violet 19, C.I. I. And CI Pigment Violet 23.

  Examples of the pigment for orange or yellow ink include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment Yellow 14C. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 155, C.I. I. And CI Pigment Yellow 180.

  Examples of pigments for green ink or cyan ink include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment green 7, C.I. I. And CI Pigment Green 36.

  Examples of the pigment for black ink include C.I. I. Pigment black 7 (carbon black), C.I. I. Pigment black 11, C.I. I. Pigment black 1 and the like. Examples of the pigment for white ink include C.I. I. Pigment white 6, C.I. I. Pigment white 18, C.I. I. And CI Pigment White 21. In addition to these coloring pigments, bright pigments such as pearl pigments and metallic pigments can also be used.

  The textile ink jet ink composition of the present invention can use dyes and pigments having relatively low light resistance in order to improve the light resistance of the printed part. That is, even if it is excellent in hue, saturation, and brightness and useful for improving color reproducibility, it is particularly effective for a color material for which fading has been a concern. For example, pigments may be used in curtains and summer clothing exposed to sunlight. In this case, a situation may occur in which a pigment having low light resistance progresses by fading due to sunlight, and a pigment having high light resistance hardly undergoes fading. Therefore, in order to suppress the fading of the pigment having low light resistance and maintain the color tone of the printed portion, it is preferable to use a pigment having relatively low light resistance for the ink of the present embodiment. Examples of pigments having relatively low light resistance include C.I. I. Pigment orange 64, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 155, C.I. I. Disazo pigments such as CI Pigment Yellow 180; I. Azomethine pigments such as C.I. Pigment Yellow 150; I. Pigment red 179, C.I. I. Perylene pigments such as C.I. Pigment Red 224, C.I. I. Perinone pigments such as C.I. Pigment Orange 43; I. Isoindolinone pigments such as CI Pigment Yellow 109; I. Quinophthalone pigments such as C.I. Pigment Yellow 138; I. Pigment green 7, C.I. I. Phthalocyanine pigments such as CI Pigment Green 36; I. Anthraquinone pigments such as C.I. Pigment Red 177; I. Pigment red 254, C.I. I. Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 71; I. Quinacridone pigments such as C.I. Pigment Violet 19; I. And dioxazine pigments such as CI Pigment Violet 23 and dye lake pigments. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 254, C.I. I. Pigment violet 19, C.I. I. Pigment Violet 23 tends to be inferior in light resistance, and is particularly suitable for the textile printing ink-jet ink composition of the present invention.

  Among the pigments described above, the phthalocyanine pigment may be inferior in light resistance, and the green color ink is more easily perceived as a fading change than other colors. Therefore, among the pigments described above, C.I. I. Pigment green 7, C.I. I. It is particularly preferable to use at least one selected from Pigment Green 36. By improving the light resistance of the ink using these pigments, it is possible to suppress the change in fading and keep the appearance of the printed portion good.

  The color material mentioned above may be used individually by 1 type, and may mix and use 2 or more types. When a pigment is used, the average particle diameter of the pigment particles is not particularly limited, but is preferably 20 nm or more and 500 nm or less. More preferably, it is 30 nm or more and 350 nm or less. By setting the average particle diameter within the above range, it is possible to ensure the color developability of the printed portion and the ejection stability of the ink from the inkjet head.

  Although the content of the color material contained in the ink of the present embodiment varies depending on the color material, in order to ensure good color developability and the ejection stability and reliability of the ink jet head (hereinafter also simply referred to as the head). The content is preferably 1% by mass or more and 30% by mass or less based on the total mass of the ink. More preferably, they are 2 mass% or more and 15 mass% or less, More preferably, they are 3 mass% or more and 10 mass% or less.

  When a pigment is used as the color material, it is preferable to surface-treat the pigment or add a dispersant or the like in order to improve dispersibility in the ink. The surface treatment of the pigment is a method of introducing a hydrophilic group such as a carboxy group or a sulfone group on the pigment surface by physical treatment or chemical treatment. The pigment surface treatment makes it possible to disperse the pigment in an aqueous solvent.

  The dispersant has an action of adsorbing the hydrophobic part (hydrophobic group) in the molecular structure on the surface of the pigment particle and orienting the hydrophilic part (hydrophilic group) on the solvent side (medium side). This action makes it possible to disperse the pigment in an aqueous solvent. As the dispersant, a known surfactant or resin can be used. Moreover, you may use the method of coat | covering pigment particles with resin etc. and providing a dispersibility. As a method for coating the pigment particles, an acid precipitation method, a transfer emulsification method, a miniemulsion polymerization method, or the like can be adopted.

<Resin dispersion>
The resin dispersion contained in the ink of the present embodiment is preferably a water-based resin dispersion in which fine resin particles are dispersed in an aqueous solvent. A resin emulsion may be used as the resin dispersion. As a resin dispersion method, a forced emulsification type using an emulsifier (surfactant), a self-emulsification type in which a hydrophilic part (hydrophilic group) is introduced into the resin molecular structure, or the like can be used. In the forced emulsification type dispersion, the surfactant may remain in the printed part and the washing fastness may be lowered. Therefore, it is more preferable to use a self-emulsification type resin dispersion.

  By blending the resin dispersion into the ink, a resin film is formed in the vicinity of the fabric surface of the printing portion. This is because if the solvent of the ink is volatilized from the textile printing portion where the ink has been applied, the resin particles are fused together to form a film. Therefore, it is preferable to dry the printed portion at a minimum film forming temperature that is the lower limit of the temperature at which the resin forms a film. The minimum film forming temperature of the resin dispersion of the present embodiment is preferably 0 ° C. or lower, more preferably −10 ° C. or lower, and further preferably −80 ° C. or lower.

  Further, in the resin film, the glass transition point of the resin of the resin dispersion is preferably 0 ° C. or lower in order to prevent breakage and cracks and to ensure the fastness to washing and abrasion resistance. More preferably, it is -10 degrees C or less, More preferably, it is -80 degrees C or less.

  The content of the resin dispersion is preferably 2% by mass or more and 25% by mass or less based on the total mass of the ink in terms of solid content. More preferably, it is 4 mass% or more and 15 mass% or less, More preferably, it is 5 mass% or more and 11 mass% or less. By setting the content of the resin dispersion within the above range, the nozzle clogging of the head can be reduced to ensure the reliability of the ink jet printer and improve the abrasion resistance of the printed portion.

  Examples of the resin used for the resin dispersion include acrylic resins, styrene / acrylic resins, fluorene resins, urethane resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, and epoxy. Resin, vinyl chloride resin, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, and the like. These resins may be used alone or in combination of two or more. Among these, it is more preferable to use urethane resin. Since the urethane-based resin has a hard segment and a soft segment in the basic skeleton, it is easy to ensure flexibility and abrasion resistance of the printed portion.

  The urethane resin is not particularly limited as long as it has a urethane group and a hydrophilic portion in the molecular structure and is an aqueous dispersion. Examples of such urethane resins include Superflex 460, 460s, 840 (above trade name, Daiichi Kogyo Seiyaku Co., Ltd.), Resamine D-1060, D-2020, D-4080, D-4200, D-. 6300, D-6455 (above trade name, Dainichi Seika Kogyo Co., Ltd.), Takerak WS-6021, W-512-A-6 (above trade name, Mitsui Chemicals Polyurethane Co., Ltd.), Sancure 2710 (above trade name, Commercial products such as LUBRIZOL) may also be used.

  The urethane-based resin is preferably an anionic urethane-based resin having an anionic functional group such as a carboxy group, a sulfone group, or a hydroxy group in order to ensure the storage stability of the ink. Examples of the anionic urethane resin include Superflex 460, 460s, 840 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Takelac WS-6021, W-512-A-6 manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and the like. .

  Furthermore, in addition to the urethane group, as the urethane resin, a polyether type urethane resin having an ether bond in the basic skeleton, a polyester type urethane resin having an ester bond in the basic skeleton, and a polycarbonate type urethane having a carbonate bond in the basic skeleton Resins can also be used. These urethane resins may be used alone or in combination.

<Ultraviolet absorber>
The ultraviolet absorber contained in the ink of the present embodiment is preferably an organic ultraviolet absorber. Since organic ultraviolet absorbers have a wider ultraviolet absorption wavelength range than inorganic ultraviolet absorbers, light resistance of color materials having various molecular structures can be improved. As such an ultraviolet absorber, a benzotriazole compound or a triazine compound can be used. The ultraviolet absorbers listed below may be used singly or in combination of two or more.

  The content of the ultraviolet absorber is preferably 0.3% by mass or more and 7.0% by mass or less based on the total mass of the ink in terms of solid content. More preferably, it is 0.3 mass% or more and 5.0 mass% or less, More preferably, it is 0.8 mass% or more, 5.0 mass% or less, More preferably, it is 1.0 mass% or more, It is 2.0 mass% or less. By setting the content of the ultraviolet absorber within the above range, it is possible to ensure the light resistance of the printed portion and to suppress an increase in ink viscosity and coloring of the coating film.

  Although it does not specifically limit as a ultraviolet absorber of a benzotriazole type compound, For example, TINUVIN PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130 (above a trade name, BASF), Chemisorb 71 Chemisorb 73, Chemisorb 74, Chemisorb 79, Chemisorb 279 (above trade name, Chemipro Kasei Co., Ltd.), ADK STAB LA-29, ADK STAB LA-31, ADK STAB LA-32, ADK STAB LA-36 (above trade names, ADEKA Corporation) Companies).

  The ultraviolet absorber of the triazine compound is not particularly limited. Company), ADK STAB LA-46, ADK STAB LA-F70 (above, trade name, ADEKA Corporation) and the like.

  In addition to the above ultraviolet absorbers, benzophenone compounds, benzoate compounds, and the like can be used alone or in combination with the above-described compounds. Although it does not specifically limit as a benzophenone series compound, For example, Chemisorb 10, Chemisorb 11, Chemisorb 12, Chemisorb 111 (above a trade name, Chemipro Kasei Co., Ltd.), Adekastab 1413 (A trade name, ADEKA Co., Ltd.) It is done. Although it does not specifically limit as a benzoate type compound, For example, Chemisorb 112, Chemisorb 113, Chemisorb 114 (above a trade name, Chemipro Kasei Co., Ltd.) etc. are mentioned.

  Moreover, you may use an inorganic type ultraviolet absorber individually or in combination with the above-mentioned thing. Examples of the inorganic ultraviolet absorber include titanium dioxide, zinc oxide, cerium dioxide and the like.

<Light stabilizer>
As the light stabilizer contained in the ink of the present embodiment, a hindered amine compound can be used. The light stabilizers listed below may be used singly or in combination of two or more.

  The content of the light stabilizer is preferably 0.3% by mass or more and 7.0% by mass or less based on the total mass of the ink in terms of solid content. The content is more preferably 0.5% by mass or more and 5.0% by mass or less, and further preferably 1.0% by mass or more and 4.0% by mass or less. By making the content of the light stabilizer within the above range, it is possible to ensure the light resistance of the printed portion and to suppress an increase in ink viscosity and coloring of the coating film.

  The light stabilizer of the hindered amine compound is not particularly limited. 94 (above trade name, Chemipro Kasei Co., Ltd.), ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-81 ADEKA Co., Ltd.).

  Among the ultraviolet absorbers and light stabilizers described above, those that are water dispersions or water-soluble are more preferred. By dissolving or dispersing in an aqueous solvent containing water, the ultraviolet absorber or the light stabilizer becomes difficult to settle in the ink. For this reason, the uniformity of the ultraviolet absorber or the light stabilizer in the ink is improved, and it is uniformly distributed in the printed portion, thereby suppressing the variation in light resistance. Further, the sedimentation thereof is suppressed, and the blockage of the ink flow path and the like is reduced. As a result, ink ejection stability and reliability are ensured.

  Furthermore, since it is easier to impart water dispersibility to form an aqueous dispersion than to make the ultraviolet absorber and the light stabilizer water-soluble, use the ultraviolet absorber and light stabilizer of the aqueous dispersion. It is even more preferable. Thereby, the selection range of the ultraviolet absorber and the light stabilizer can be expanded.

  In order to make an ultraviolet absorber and a light stabilizer into an aqueous dispersion, a method by self-emulsification by introducing a hydrophilic portion (hydrophilic group) into their molecular structure, a method by forced emulsification using an emulsifier (surfactant), A method including a resin having a dispersant function can be employed. A resin having an emulsifier or dispersant function has a hydrophobic portion and a hydrophilic portion (hydrophilic group) in the molecular structure. The hydrophobic part is adsorbed on the surface of the ultraviolet absorber or the light stabilizer, and the hydrophilic part (hydrophilic group) is oriented to the aqueous medium side, thereby exhibiting water dispersibility. The hydrophilic group is not particularly limited, and examples thereof include a sulfone group, a carboxy group, a carbonyl group, a hydroxy group, a phosphate group, a quaternary ammonium, and a salt thereof.

Examples of the UV absorber for the aqueous dispersion include TINUVIN 99-DW, TINUVIN 400-DW, TINUVIN 477-DW, TINUVIN 479-DW (above trade name, BASF), Chemisorb 11S (above trade name, Chemipro Kasei Co., Ltd.) Company).
Examples of the light stabilizer of the aqueous dispersion include TINUVIN 123-DW and TINUVIN 5333-DW (trade name, BASF).
By using a combination of at least one UV absorber and a light stabilizer in the water dispersion described above, it is possible to improve the light fastness of the printed part while ensuring the ejection stability and reliability of the ink. it can.

  It is sufficient that at least one of the ultraviolet absorber and the light stabilizer is contained. However, the inclusion of the ultraviolet absorber and the light stabilizer is preferable because the effect of the present invention can be further improved. When the ultraviolet absorber and the light stabilizer are contained, the total content is preferably 9% by mass or less, more preferably 5% by mass or less, based on the total mass of the ink in terms of solid content. By setting the total content in such a range, it is possible to ensure the light resistance of the printed portion and to more suitably suppress the increase in ink viscosity and coloring of the coating film.

<Water>
Water is the main medium of the ink of this embodiment. When printing is performed, water evaporates and scatters by drying from the printing unit. As water, for example, water from which ionic impurities such as ion-exchanged water, ultrafiltered water, reverse osmosis water, distilled water, and ultrapure water are removed as much as possible can be used. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the ink is stored for a long period of time. The content of water contained in the ink is not particularly limited, but is preferably 50% by mass or more and 95% by mass or less with respect to the total mass of the ink.

<Organic solvent>
An organic solvent may be added to the ink of this embodiment. By adding an organic solvent, it is possible to control ink physical properties such as viscosity and surface tension, and ink behavior such as drying and penetration on a fabric.
Examples of the organic solvent include 2-pyrrolidones, 1,2-alkanediols, polyhydric alcohols, glycol ethers, and the like. These can be used alone or in combination of two or more.

  2-Pyrrolidones refer to compounds having a 2-pyrrolidone skeleton. Examples of 2-pyrrolidones include substituents such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-vinyl-2-pyrrolidone in addition to 2-pyrrolidone having no substituent. A compound having can be used. The substituent in the 2-pyrrolidone skeleton is preferably an organic group having 1 to 5 carbon atoms such as a saturated or unsaturated hydrocarbon group. Among these, it is more preferable to use 2-pyrrolidone which is excellent in the storage stability of ink and the effect of suppressing the generation of aggregates.

  When 2-pyrrolidone is added, the content is preferably 0.9% by mass or more and 8.1% by mass or less with respect to the total mass of the ink. More preferably, it is 1 mass% or more and 8 mass% or less. By controlling the content of 2-pyrrolidones within the above range, the generation of aggregates due to the resin is suppressed, and the ink viscosity is kept within an appropriate range, which will be described later, and the ink ejection stability is improved. Can do.

  Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, and the like. . 1,2-Alkanediols are excellent in the action of increasing the wettability of the ink with respect to a recording medium such as a fabric to wet it uniformly. Therefore, an image with less bleeding can be printed. The content in the case of adding 1,2-alkanediols is preferably 1% by mass or more and 20% by mass or less with respect to the total mass of the ink.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl- Examples include 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, trimethylolpropane, and glycerin. By adding polyhydric alcohols to the ink, it is possible to suppress drying and solidification of the ink in the nozzles of the head, and to reduce nozzle clogging or ejection failure. When polyhydric alcohols are added, the content is preferably 2% by mass or more and 20% by mass or less with respect to the total mass of the ink.

  Examples of glycol ethers include alkylene glycol monoether and alkylene glycol diether.

  Examples of the alkylene glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl. Ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

  Examples of the alkylene glycol diether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol di Chirueteru, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

  By adding glycol ethers to the ink, the wettability and permeation speed of the ink with respect to a recording medium such as a fabric can be adjusted, so that an image or a pattern can be printed clearly. The content in the case of adding glycol ethers is preferably 0.05% by mass or more and 6% by mass or less with respect to the total mass of the ink.

<Other ingredients>
As the other components, a surfactant, a pH adjuster, a preservative, a fungicide, a crosslinking agent, and the like may be added to the ink of the present embodiment.

  The surfactant has a function of reducing the surface tension of the ink and improving the wettability with respect to a recording medium such as a fabric. As the surfactant, for example, an acetylene glycol surfactant, a silicone surfactant, a fluorine surfactant, or the like can be used.

  Although it does not specifically limit as acetylene glycol type surfactant, For example, Surfynol 104,104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50,104S, 420,440,465,485, SE, SE- F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (above trade names, Air Products and Chemicals, Inc.), Olfin B, Y, P, A, STG, SPC, E1004 E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (above trade names, Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (above trade names, Kawaken Fine Chemical Co., Ltd.) ) And the like.

  Although it does not specifically limit as a silicone type surfactant, It is preferable to use a polysiloxane type compound. Although it does not specifically limit as a polysiloxane compound, For example, polyether modified organosiloxane is mentioned. Commercially available products of polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, BYK), KF -351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF -6011, KF-6012, KF-6015, KF-6017 (above trade names, Shin-Etsu Chemical Co., Ltd.) and the like.

  As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer. For example, BYK-340 (the above-mentioned brand name, BYK company) etc. are mentioned.

  Although it does not specifically limit as a pH adjuster, For example, an organic base and an inorganic base are mentioned. It is preferable to adjust the pH of the ink to a range of 7.5 or higher and 10.5 or lower using these pH adjusters.

  Examples of the organic base include alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, and tri-iso-propanolamine. Here, in order to bring the pH of the ink within the above range using these organic bases, it is necessary to add a relatively large amount. Specifically, for example, it is about 0.1% by mass to 3% by mass with respect to the total mass of the ink.

  As the inorganic base, for example, a strong base that is a hydroxide of an alkali metal or alkaline earth metal such as lithium hydroxide, potassium hydroxide, or calcium hydroxide can be used. In order to bring the pH of the ink within the above range using these inorganic bases, for example, about 0.03% by mass or more and 0.15% by mass or less may be added with respect to the total mass of the ink. As described above, it is more preferable to use an inorganic base because the amount of the inorganic base added is smaller than that of the organic base and there is no odor like the organic base.

  By adding a preservative or fungicide to the ink, it is possible to suppress the growth of bacteria and fungi in the ink. Examples of antiseptics and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzthiazolin-3-one ( LONZA brand names PROXEL CRL, PROXEL BDN, PROXEL GXL, PROXEL XL-2, PROXEL TN) and the like.

  The crosslinking agent reacts with a hydroxyl group, a carboxy group, or the like included in the resin dispersion to form a crosslinked structure, and can improve the strength of the film formed by the resin dispersion. As such a crosslinking agent, a blocked isocyanate compound, a carbodiimide compound, or the like can be used.

<Ink>
The ink according to the present embodiment can be prepared by mixing the above-described components in an arbitrary order, and performing filtration or the like as necessary to remove impurities and foreign matters. As a method for mixing each component, a method in which materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is used. As a filtration method, centrifugal filtration, filter filtration, or the like can be employed.

  The viscosity of the ink is preferably 1 mPa · s or more and 7 mPa · s or less at 25 ° C. More preferably, it is 2 mPa · s or more and 5.5 mPa · s or less. By setting the viscosity of the ink within the above range, it is possible to ensure the ejection stability and ejection amount of the ink from the head. When the viscosity is out of the above range, the ink ejection stability may be ensured by changing the ink ejection conditions and the head type in the head. For example, 22 mP · In some cases, ejection stability can be ensured up to a. The ink viscosity can be measured by using a DVM-E rotational viscometer (Tokyo Keiki Co., Ltd.) and adjusting the ink temperature to 25 ° C.

<Inkjet printing device>
Next, the inkjet textile printing apparatus according to the present embodiment will be described with reference to FIG. The ink-jet printing apparatus is an apparatus that performs printing by causing droplets to land on a textile printing portion by an ink-jet method that ejects minute liquid droplets of ink. FIG. 1 is a schematic perspective view illustrating an inkjet printing apparatus according to the first embodiment. In the present embodiment, an on-carriage type printer in which an ink cartridge is mounted on a carriage will be described as an example of an ink jet textile printing apparatus. In FIG. 1, the scale of each member is different from the actual scale so that each member can be recognized.

  The printer 1 of this embodiment is a so-called serial printer. A serial printer is a printer in which a head is mounted on a carriage that moves in a predetermined direction, and printing is performed while the head moves as the carriage moves.

  As shown in FIG. 1, the printer 1 includes a head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the operation of the entire printer 1. The carriage 4 has the head 3 mounted thereon, and ink cartridges 7 a, 7 b, 7 c, 7 d, 7 e, and 7 f that store ink supplied to the head 3 are detachable.

  The main scanning mechanism 5 includes a timing belt 8 connected to the carriage 4, a motor 9 that drives the timing belt 8, and a guide shaft 10. The guide shaft 10 is installed as a support member for the carriage 4 in the scanning direction (main scanning direction) of the carriage 4. The carriage 4 is driven by a motor 9 via a timing belt 8 and can reciprocate along a guide shaft 10. Thus, the main scanning mechanism 5 has a function of reciprocating the carriage 4 in the main scanning direction.

  The platen roller 6 has a function of conveying the recording medium 2 as a fabric to be printed in the sub-scanning direction (length direction of the recording medium 2) perpendicular to the main scanning direction. Therefore, the recording medium 2 is conveyed in the sub scanning direction. In addition, the carriage 4 on which the head 3 is mounted can reciprocate in the main scanning direction that substantially coincides with the width direction of the recording medium 2, and the head 3 moves relative to the recording medium 2 in the main scanning direction and the sub-scanning direction. Scanning is relatively possible.

  The ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f are six independent ink cartridges. The ink-jet cartridges 7a, 7b, 7c, 7d, 7e, and 7f can store the above-described textile printing ink-jet ink composition (ink). These ink cartridges individually store inks having colors such as black, cyan, magenta, yellow, violet, green, and orange and can be used in any combination. In FIG. 1, the number of ink cartridges is six, but the present invention is not limited to this. At the bottom of the ink cartridges 7a, 7b, 7c, 7d, 7e, 7f, supply ports (not shown) for supplying the ink stored in the ink cartridges to the head 3 are provided.

  The head 3 has a nozzle surface (not shown) on the surface facing the recording medium 2. On the nozzle surface, a nozzle row (not shown) composed of a plurality of nozzles (not shown) is individually arranged corresponding to each color ink. Each color ink is supplied from each ink cartridge to the head 3 and is ejected as a droplet from the nozzle by an actuator (not shown) in the head 3. The ejected ink droplets land on the recording medium 2 to form an image, text, pattern, color, or the like on the printing portion of the recording medium 2.

  Here, the head 3 uses a piezoelectric element as an actuator (driving means), but is not limited to this method. For example, an electromechanical conversion element that displaces a diaphragm as an actuator by electrostatic adsorption, or an electrothermal conversion element that discharges ink as droplets by bubbles generated by heating may be used.

  In the present embodiment, the on-carriage type printer 1 is exemplified as the ink jet textile printing apparatus, but the present invention is not limited to this. For example, an ink carriage such as an ink cartridge may be an off-carriage type printer that is not mounted on a carriage. Further, the ink jet printing apparatus used in the present invention is not limited to the above-described serial printer, and a line head in which the head is formed wider than the width of the recording medium 2 and printing is performed without moving the head. It may be a printer.

  The recording medium 2 used for the ink of the present embodiment is preferably a fabric. Examples of the fabric include fabric, clothing, and other clothing items. Examples of the fabric include woven fabrics, knitted fabrics, and nonwoven fabrics using natural fibers such as cotton, silk, and wool, chemical fibers such as nylon and polyester, or fibers obtained by blending these. For clothing and other apparel, as well as furniture items such as T-shirts after sewing, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, sheets, bedspreads, wallpaper, etc. This includes cloth before and after cutting. As these forms, a long thing wound by roll shape, the thing cut | disconnected by the predetermined magnitude | size, the thing of a product shape, etc. are mentioned.

<Inkjet recording method>
Next, an ink jet recording method using the ink according to this embodiment will be described. In the ink jet recording method of the present embodiment, printing is performed by using the above-described printer 1 (see FIG. 1) to eject ink droplets by the ink jet method and applying the ink droplets onto a cloth or the like to form an image or the like. Is.

As a pre-process for ink application, a process for applying a pretreatment agent to the fabric may be provided. By adding a polyvalent metal compound to the pretreatment agent, the polyvalent metal compound reacts with the resin component in the ink and aggregates to promote resin film formation. The polyvalent metal compound is a compound containing a divalent or higher polyvalent metal ion and an anion. Examples of the divalent or higher polyvalent metal ions include Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ , Ba ²⁺ , and Al ³⁺ . Examples of the anion include Cl ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , I ⁻ , Br ⁻ , ClO ₃ ^{− and the} like. Among these, it is preferable to use a magnesium salt, a calcium salt, or an aluminum salt, which has a high aggregation effect. In addition to these, the effect of aggregation can also be obtained by using organic acids, polyallylamine, and polyallylamine derivatives.

  In addition, pretreatment agents include resins, surfactants, pastes (eg, starches, celluloses, polysaccharides, proteins, water-soluble polymer compounds, etc.), organic acids, water, pH adjusters, preservatives and anti-preventive agents. It may contain fungicides and the like. Although it does not specifically limit as resin, For example, well-known resin, such as an acrylic resin, a styrene-acrylic resin, a fluorene resin, a urethane-type resin, a polyolefin-type resin, an ethylene-vinyl acetate copolymer, can be used.

  In the ink application process, as described above, an image, text, pattern, color, and the like are formed on the printing portion of the recording medium 2 (fabric) by the ink droplets ejected from the head 3 (see FIG. 1). .

  A heating process for heating the fabric may be provided as a subsequent process of the ink application process. The heating step is a step of drying the ink applied to the fabric. As a result, the resin contained in the ink is formed into a film to form a film, thereby improving the abrasion resistance of the printed portion. At this time, the light resistance of the color material is improved by incorporating the color material and the ultraviolet absorber or light stabilizer into the film. Although it does not specifically limit as a heating method in a heating process, For example, a heat press method, a normal pressure steam method, a high pressure steam method, a thermofix method etc. are mentioned. For example, an infrared lamp can be used as a heat source for heating. The temperature of the heat treatment is not particularly limited as long as the resin contained in each color ink can be fused and moisture can be evaporated, and can be, for example, about 100 ° C. or higher and about 200 ° C. or lower.

  Further, after the heating step, a step of washing and drying the printed fabric may be provided. In washing with water, if necessary, as a soaping treatment, unfixed color materials that have not been taken into the resin film may be washed away using a hot soap solution or the like.

As described above, according to the ink and the ink jet recording method according to the present embodiment, the following effects can be obtained.
According to the ink of the present embodiment, the resin dispersion and the ultraviolet absorber or the light stabilizer are contained in the water-based ink, so that even when exposed to sunlight or the like for a long time, the color fading occurs in the printed portion. Can be suppressed. Specifically, when a fabric is printed by an inkjet method, the resin dispersion in the ink forms a resin film near the fabric surface. By being included in this film, the coloring material and the ultraviolet absorber or light stabilizer are less likely to penetrate into or between the fibers of the fabric. Therefore, the coloring material and the ultraviolet absorber or light stabilizer stay on the fabric surface and come close to each other. Since the color material and the ultraviolet absorber or light stabilizer are present in the vicinity, fading of the color material due to sunlight or the like can be effectively suppressed. In addition, the color material is protected by the above-described film during washing, and color fading due to the color material falling off is suppressed. As a result, discoloration and discoloration due to exposure to sunlight and washing and washing are suppressed, and the appearance of the printed part is unlikely to deteriorate. That is, it is possible to provide a printed inkjet ink composition having improved light resistance and washing fastness.

  Furthermore, the deterioration of the resin film itself can be suppressed by the ultraviolet absorber or the light stabilizer. Specifically, the heat treatment in the post-printing process described above and exposure to sunlight during use may cause deterioration of the film. Deterioration or fading of the resin induced by the manufacturing process or use environment can be suppressed by the action of the ultraviolet absorber or the light stabilizer. And since an ultraviolet absorber or a light stabilizer is also included in the film of the resin, even if the fabric is washed, the outflow and dropout of them are reduced, and the effect of the ultraviolet absorber or the light stabilizer can be maintained. it can.

  According to the ink jet recording method of this embodiment, it is possible to improve the light resistance of recording of images, texts, patterns, colors, etc. on a recording medium. Further, the ink can be applied as fine droplets by using an inkjet method. Thereby, compared with methods other than the inkjet method, high resolution recording can be obtained, and aesthetics can be improved.

  The effects of the present embodiment will be described more specifically below by showing Examples and Comparative Examples in which the ink viscosity, light resistance, washing fastness, and abrasion resistance are evaluated for the ink of the present embodiment.

<Preparation of pigment dispersion>
(1) Preparation of Green Pigment Dispersion 1 After mixing and stirring 80.5 parts by mass of ion exchange water with 1.5 parts by mass of 30% by mass ammonia aqueous solution (neutralizing agent), acrylic acid-acrylic as a resin dispersant 8 parts by mass of an acid ester copolymer (weight average molecular weight 25000, acid value 180) was added and dissolved. There, C.I. I. 10 parts by weight of Pigment Green 36 was added, and dispersion treatment was performed for 10 hours with a ball mill using zirconia beads to obtain Green Pigment Dispersion Liquid 1 having a pigment concentration of 10% by weight.

(2) Preparation of Green Pigment Dispersion 2 Green Pigment Dispersion 2 was prepared as C.I. I. Pigment Green 36, C.I. I. A green pigment dispersion 2 having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment green 7 was used.

(3) Preparation of Orange Pigment Dispersion In the method for preparing Green Pigment Dispersion 1, the orange pigment dispersion is C.I. I. Pigment Green 36, C.I. I. An orange pigment dispersion having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment orange 64 was used.

(4) Preparation of Cyan Pigment Dispersion Cyan pigment dispersion was prepared as C.I. I. Pigment Green 36, C.I. I. A cyan pigment dispersion having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment blue was changed to 15: 3.

(5) Preparation of Yellow Pigment Dispersion In the method for preparing the green pigment dispersion 1, the yellow pigment dispersion is C.I. I. Pigment Green 36, C.I. I. A yellow pigment dispersion having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment yellow 138 was used.

(6) Preparation of Red Pigment Dispersion Liquid Red pigment dispersion liquid was prepared as C.I. I. Pigment Green 36, C.I. I. A red pigment dispersion having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment red 177 was used.

(7) Preparation of Violet Pigment Dispersion Violet pigment dispersion is a C.I. I. Pigment Green 36, C.I. I. A violet pigment dispersion having a pigment concentration of 10% by mass was obtained in the same manner except that the pigment violet 23 was used.

<Ink adjustment>
The compositions of the inks of Examples 1 to 24 and Comparative Examples 1 to 5 are shown in Tables 1 and 2. In the present invention, the content ratio of the ultraviolet absorber, light stabilizer, and resin dispersion refers to the content (unit: mass%) of the active ingredient (solid content) with respect to the total mass of the ink. In Table 1 and Table 2, the unit of numerical values in the table is mass%, and the content of active ingredients (solid content) other than the solvent, surfactant and ion-exchanged water is indicated. Further, the ion exchange water was adjusted and added so that the total mass of the ink was 100% by mass. About each Example and each comparative example, according to the composition of the ink shown in Table 1 and Table 2, each component was put into the container, and it mixed and stirred for 2 hours using the magnetic stirrer. Subsequently, the mixed liquid was filtered through a membrane filter having a pore diameter of 5 μm to obtain inks of Examples and Comparative Examples.

In Tables 1 and 2, the components described other than the compound names in addition to the pigment dispersion are as follows.
<Color material>
Acid dye C.I. I. Acid Blue 90 ((Reagent, Tokyo Chemical Industry Co., Ltd., CAS No .: 6104-58-1))
<Resin dispersion>
・ Takelac WS-6021 (trade name, Mitsui Chemicals Polyurethanes Co., Ltd., anionic urethane resin dispersion, solid content concentration of 30% by mass)
・ Viniblanc 2650 (trade name, Nissin Chemical Industry Co., Ltd., acrylic ester resin dispersion, solid content 40% by mass)
<Ultraviolet absorber>
TINUVIN 400-DW (trade name, BASF, triazine compound, aqueous dispersion, solid content concentration 20% by mass)
TINUVIN 99-DW (trade name, BASF, benzotriazole-based compound, aqueous dispersion, solid content concentration of 24% by mass)
・ TINUVIN 99-2 (trade name, BASF, benzotriazole compound, water-soluble and water-dispersible)
<Light stabilizer>
TINUVIN 123-DW (trade name, BASF, hindered amine compound, aqueous dispersion, solid content concentration 30% by mass)
<Others>
・ BYK-348 (trade name, BYK, silicone surfactant)

  Examples 1 to 10 and Examples 15 to 19 are C.I. I. Pigment Green 36 (Green Pigment Dispersion Liquid 1) was used. In other embodiments, C.I. I. Pigment Green 7 (Green Pigment Dispersion Liquid 2) or other colorant was used, and in particular, in Examples 13 and 14, an acid dye was used. In Examples 5 to 7, and Example 17, only the light stabilizer was used without using the ultraviolet absorber. In Examples 1 to 4, Example 15 and 16, and Examples 18 to 20, only the ultraviolet absorber was used without using the light stabilizer. In other examples, an ultraviolet absorber and a light stabilizer were used in combination.

  Here, taking Example 8 as an example, the notation of Table 1 will be described. As described above, in Table 1, the numerical values of the ultraviolet absorber, the light stabilizer, and the resin dispersion are represented by the content ratio of the active ingredient (solid content). Similarly, the pigment dispersion is also expressed by the content ratio of the pigment which is an active ingredient. Therefore, the content ratio 4% by mass of the green pigment dispersion 1 of Example 8 indicates the pigment content ratio. That is, the actual blending amount of the green pigment dispersion 1 into the ink is 40% by mass. The same notation is used for the resin dispersion, the ultraviolet absorber, and the light stabilizer. Therefore, the content of 5% by mass of the resin dispersion (Takelac WS-6021, aqueous dispersion having a solid content of 30% by mass) is a numerical value of the solid content, and the amount of the resin dispersion added to the ink is 17% by mass. It becomes. Similarly, the actual blending amount in the ink is 5% by mass of the ultraviolet absorber (TINUVIN 400-DW, an aqueous dispersion having a solid concentration of 20% by mass) (the content of the active ingredient is 1% by mass), and the light stabilizer ( TINUVIN123-DW, an aqueous dispersion having a solid content concentration of 30% by mass) is 2% by mass (the active ingredient content is 0.6% by mass). Acid dye C.I. I. Since Acid Blue 90 and TINUVIN 99-2 are not dispersions, the content ratio in ink and the actual blending amount are equivalent.

  Comparative Examples 1 and 2 are C.I. I. Pigment Green 36 (Green Pigment Dispersion Liquid 1) was used. In other comparative examples, other coloring materials were used, and in particular, in Comparative Examples 4 and 5, acid dyes were used. In Comparative Example 1, Comparative Example 3, and Comparative Example 4, neither an ultraviolet absorber nor a light stabilizer was used. In Table 2, the same notation system as in Table 1 is used.

<Viscosity measurement>
For the inks for evaluation in each of the examples and comparative examples, the viscosity of the ink at 25 ° C. was measured immediately after it was prepared by the method described above. The results are shown in Table 3. In Table 3, those having a viscosity of 2 mPa · s or more and 7 mPa · s or less are “good”, 1 mPa · s or more and less than 2 mPa · s, or more than 7 mPa · s and 9 mPa · s or less. Were evaluated as “x (unsuitable)” when “Δ (allowable)”, less than 1 mPa · s or more than 9 mPa · s.

<Light resistance evaluation>
About the ink for evaluation of each Example and each comparative example, the textile was printed by the following method, and the light resistance was evaluated about the printing part.
Using an ink jet printer (Seiko Epson Corporation, trade name: MJ-3000C), the ink of each example and each comparative example was applied to a 20 cm square area of a fabric (HANES, heavy weight, 100% cotton white fabric). Printed. The ink application conditions of the inkjet printer were a recording resolution of 1440 dpi (dot per inch) × 1440 dpi, a solid pattern image was applied, and 20 mg of ink was applied per square inch. Here, the solid pattern image refers to an image in which ink droplets (dots) are landed on all the pixels that are the minimum recording unit area defined by the recording resolution.

  Next, the printed fabric was subjected to a heat treatment at 160 ° C. for 1 minute using a heat press. For Examples 13 and 14, and Comparative Examples 4 and 5 using an acid dye, steaming was performed for 30 minutes under high humidification conditions at a temperature of 102 ° C. using a steamer DHe type (Matis Co., Ltd.) as the heat treatment. Treated. Further, after the steaming treatment, after scouring with tap water, it was immersed in warm water of about 50 ° C. to which a nonionic soap was added for about 15 minutes with occasional stirring. Then, it was rinsed thoroughly, dried and ironed.

  About the ink of each Example and each comparative example, it printed by the method mentioned above and produced the test piece for light resistance. Using this test piece, a light resistance test was carried out using a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with the fifth exposure method of JIS L 0843 (Testing method for dyeing fastness to xenon arc lamp). did. The results are shown in Table 3. In Table 3, “◎ (preferred)” indicates that the evaluation result exceeds 4th grade, “○ (suitable)” for 4th grade, and “△ (allowable) for grade 3 to less than 4th grade. ) ”Grade 3 was judged as“ ΔΔ (within allowable limits) ”and grade 3 graded as“ x (unsuitable) ”.

<Washing fastness evaluation>
The ink for evaluation of each example and each comparative example was subjected to a wash fastness test in accordance with A-2 method of JIS L 0844 (Dye fastness test method for washing). Specifically, as in the light resistance test, a fabric subjected to printing and heat treatment was produced. Next, the fabric was used as a test piece, subjected to a washing treatment, rinsed, dehydrated and dried, and then the discoloration of the printed portion of the test piece was determined. The color fading is JIS L0804: 2004 (ISO 105-A02: 1993) color fading gray scale. The degree of fading was evaluated and judged in accordance with the provision of gray scale for fading.) In addition, evaluation of the coloring contamination by an attached white cloth was abbreviate | omitted. The results are shown in Table 3. In Table 3, “◎ (preferred)” indicates that the evaluation result exceeds 4th grade, “○ (suitable)” for 4th grade, and “△ (allowable) for grade 3 to less than 4th grade. ) ”Grade 3 and below were judged as“ x (unsuitable) ”.

<Rubbing resistance evaluation>
The ink for evaluation of each Example and each Comparative Example was evaluated for rubbing resistance (friction fastness test) by the following method. Similar to the light resistance test, a fabric subjected to printing and heat treatment was produced. Next, a strip-shaped test piece for abrasion resistance was cut out from the fabric. Using the above test piece, the abrasion resistance was evaluated with a Gakushin frictional fastness tester AB-301S (trade name, Tester Sangyo Co., Ltd.). The test conditions were carried out in accordance with JIS L 0849, using an opposing cloth as a gold width, applying 150 reciprocating friction slides at a load of 200 g. Table 3 shows the test results in the drying mode (when the facing fabric is dry). In Table 3, regarding the degree of color transfer to the gold width and the ink peeling of the printed part, “◎ (preferred)”, where there is no color transfer in the gold width and there is no ink peeling or scratches on the printed part, There is a small amount of color transfer, and “○ (suitable)” means that there is no ink peeling or scratches on the printed part. In the case of “△ (allowable)”, the case where there was a large amount of color transfer in the gold width and the large-scale printed part was peeled or scratched was judged as “× (unsuitable)”. In addition, tests with “−” in the table have not been tested.

<Weather resistance evaluation>
For the evaluation inks of Example 1 and Example 5, the weather resistance was evaluated. A sample similar to that used in the light resistance evaluation was prepared and placed in the chamber of a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.). The test conditions were a cycle test of 60 W / m ² (300 nm to 400 nm) of light irradiation for 40 minutes, light irradiation and water rain for 20 minutes, light irradiation for 60 minutes, and water rain for 60 minutes. The cycle test was conducted continuously for 2 weeks, and a sample was taken out. Next, after the samples were air-dried, the degree of fading of the samples of Example 1 and Example 5 was compared. As a result, in contrast to Example 1 in which the ultraviolet absorber was used alone, Example 5 in which the light stabilizer was used alone showed better weather resistance.

  As shown in Table 3, in Examples 1 to 24, both light resistance and wash fastness are at least within acceptable limits, and in many examples both light fastness and wash fastness are excellent. It was shown that Scratch resistance and ink viscosity were within acceptable ranges in all examples. In Examples 9, 12, and 14, the components other than the color material and the content ratio thereof are the same, and the difference in the light resistance evaluation result is derived from the light resistance of the color material itself.

  In addition, in the case of an ink prepared by mixing and stirring the respective components with the same composition as in Example 18 and omitting the filtration of the mixed solution, the light resistance evaluation result is ΔΔ (within the allowable limit) of Example 18. Changed from Δ to Δ (acceptable). This difference is considered that in Example 18, a part of the ultraviolet absorber (TINUVIN 99-2) to which water-solubility and water-dispersibility were not imparted was excluded by filtration. With the above ink, the evaluation results of ink viscosity, wash fastness and abrasion resistance were the same as those in Example 18. Further, since filtration is omitted, coarse particles derived from the ink component may remain in the ink, and ink ejection from the head may become unstable.

  On the other hand, in the comparative example, either light resistance or washing fastness was judged as x (unsuitable), indicating that it was inferior to the examples.

  The present invention is not limited to the above-described embodiments, and can be changed as appropriate without departing from the spirit or idea of the invention that can be read from the claims and the entire specification. Ink with such changes ( Textile inkjet ink compositions) are also within the scope of the present invention.

  DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Recording medium, 3 ... Head, 4 ... Carriage, 5 ... Main scanning mechanism, 6 ... Platen roller, 7a, 7b, 7c, 7d, 7e, 7f ... Ink cartridge, 8 ... Timing belt, 9 ... motor, 10 ... guide shaft.

Claims (12)

Containing a resin dispersion, a coloring material, and water;
Furthermore, the textile-printing inkjet ink composition containing at least one of a ultraviolet absorber or a light stabilizer.   The textile printing ink-jet ink composition according to claim 1, comprising the ultraviolet absorber and the light stabilizer.   The color material is C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. Pigment orange 43, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment red 177, C.I. I. Pigment red 179, C.I. I. Pigment red 224, C.I. I. Pigment red 254, C.I. I. Pigment violet 19, C.I. I. The textile printing ink-jet ink composition according to claim 1, comprising at least one pigment selected from CI Pigment Violet 23.   The color material is C.I. I. Pigment green 7, C.I. I. The textile printing inkjet ink composition according to claim 1 or 2, comprising at least one pigment selected from CI Pigment Green 36.   The textile printing inkjet ink composition according to any one of claims 1 to 4, wherein at least one of the ultraviolet absorber and the light stabilizer is an aqueous dispersion.   The textile printing inkjet ink composition according to any one of claims 1 to 5, wherein the ultraviolet absorber contains at least one selected from a triazine compound and a benzotriazole compound.   The textile printing inkjet ink composition according to any one of claims 1 to 6, wherein the light stabilizer includes a hindered amine compound.   The textile printing according to any one of claims 1 to 7, wherein a content ratio of the ultraviolet absorber is 0.3% by mass or more and 5.0% by mass or less with respect to a total mass of the ink composition. Inkjet ink composition.   The printing according to any one of claims 1 to 8, wherein a content ratio of the light stabilizer is 0.3% by mass or more and 5.0% by mass or less with respect to a total mass of the ink composition. Inkjet ink composition.   The content ratio of the solid content of the resin dispersion is 2.0% by mass or more and 25.0% by mass or less based on the total mass of the ink composition. The printing inkjet ink composition as described.   The textile printing inkjet ink composition according to any one of claims 1 to 10, wherein the resin dispersion contains a urethane-based resin.   The inkjet recording method which records on a recording medium by the inkjet method using the textile-printing inkjet ink composition as described in any one of Claims 1-11.

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