WO2019107284A1 - Inkjet textile-printing composition set and method for inkjet textile printing - Google Patents

Abstract

Provided is an inkjet textile-printing composition set whereby a textile-printed article having excellent texture and friction fastness can be obtained. An inkjet textile-printing composition provided with an ink composition containing a pigment, resin particles, and water, and a coating composition containing resin particles and water, wherein the resin particles contained in the ink composition include any of a urethane-based resin, a polycarbonate resin, an acrylic-based resin, and a styrene resin, the content of the resin particles contained in the ink composition is 1-5 parts by mass in terms of solid content with respect to 1 part by mass of pigment solid content, the Young's modulus of a dried coating film of the ink composition is 1-25 MPa, and the Young's modulus of a dried coating film of the coating composition is 50 MPa or less and is higher than the Young's modulus of a dried coating film of the ink composition.

Description

Composition set for inkjet printing, and inkjet printing method

The present invention relates to an inkjet printing composition set and an inkjet printing method.

The ink jet recording method is a relatively simple apparatus and can record high definition images, and has been rapidly developed in various fields. Among them, various studies have been made to obtain more stable and high quality recorded matter.

For example, Patent Document 1 discloses a color ink and an overcoat liquid for the purpose of providing an ink jet ink having excellent print quality and ink discharge stability and high rub fastness for textiles. An inkjet ink set comprising: a color ink containing a coloring material; and an overcoat liquid containing a polyester resin and substantially containing no coloring material is disclosed.

JP, 2013-221141, A

However, when the ink set as described in Patent Document 1 is used for ink jet printing, a recording liquid containing a fabric, which is a coating liquid that is an overcoat liquid, is formed on an ink composition that is a color ink. When deposited on a medium, the resulting printed matter is excellent in rub fastness but not sufficiently good in texture.

Therefore, the present invention has been made to solve at least a part of the above-mentioned problems, and to provide a composition set for ink jet printing capable of obtaining a print having excellent feeling and fastness to rubbing. To aim.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors were provided with the ink composition containing a pigment, a resin particle, and water, and the coating composition containing resin particles and water, and an ink composition. The resin particles contained in the resin contain a predetermined resin, the content of the resin particles contained in the ink composition is in a predetermined range, and the Young's modulus of the coating obtained by drying the ink composition and the coating composition is specified respectively The present inventors have completed the present invention by finding that a print having excellent texture and rubbing fastness can be obtained by using a composition set for inkjet printing having the following relationship.

That is, the present invention is a composition set for ink jet printing comprising an ink composition containing a pigment, resin particles and water, and a coating composition containing resin particles and water, the ink composition comprising The resin particles contained in any one of urethane resin, polycarbonate resin, (meth) acrylic resin and styrene resin, and the content of the resin particles contained in the ink composition is the pigment solid content 1 The solid content is 1 to 5 parts by mass, and the Young's modulus of the coating obtained by drying the ink composition is 1 to 25 MPa, and the Young of the coating obtained by drying the coating composition is The ink jet printing composition set has a rate of 50 MPa or less and is higher than the Young's modulus of the coating obtained by drying the ink composition. The factors which can solve the problem of the present invention by such a composition set for ink jet printing are considered as follows. However, the factor is not limited to this. That is, when only the ink composition is used without using the conventional coating composition, the ink composition containing the pigment deposited on the recording medium is caused by the presence of the pigment on the surface of the ink composition. And the pigment on the surface is scraped off due to friction, etc., so that the rub fastness is not excellent. Further, the ink set containing the conventional pigment and the composition set provided with the coating composition substantially contain the pigment on the surface by depositing the ink composition and the coating composition in this order on the recording medium. Due to the presence of the coating composition which does not have a high viscosity, the fastness to rubbing is excellent. However, the conventional composition set using a coating composition having a high Young's modulus as a coating film is excellent in the fastness to rubbing, but not sufficiently good in the texture of the resulting printed matter. Moreover, although the conventional composition set at the time of using a coating composition with a low Young's modulus when it is set as a coating film is excellent in the feel, it is not sufficiently excellent in friction fastness. On the other hand, in the composition set for inkjet printing according to the present invention, the coat composition is obtained while the texture of the printed material obtained is excellent mainly because the Young's modulus of the coating film obtained by drying the coating composition is 50 MPa or less. When the Young's modulus of the dried coating is higher than the Young's modulus of the coating obtained by drying the ink composition, the resulting printed matter is also excellent in the fastness to rubbing.

Moreover, it is preferable that the composition set for inkjet textiles which concerns on this invention is equipped with the following structure further.
The Young's modulus of the coating obtained by drying the ink composition is preferably 1 to 20 MPa.
The Young's modulus of the coating obtained by drying the ink composition is preferably 5 to 20 MPa.
The Young's modulus of the coating obtained by drying the coating composition is preferably 5 to 25 MPa higher than the Young's modulus of the coating obtained by drying the ink composition.
The Young's modulus of the coating film obtained by drying the coating composition is preferably 5 to 50 MPa.
The resin particles contained in the ink composition preferably include a resin having a crosslinkable group.
The crosslinkable group more preferably contains either a blocked isocyanate group or a silanol group.
It is more preferable that the resin particles contained in the ink composition contain a urethane resin having a polycarbonate skeleton.
The content of the resin particles contained in the coating composition is preferably 0.1 to 10% by mass in solid content with respect to the total amount of the coating composition.
It is preferable that the ink composition or the coating composition further contain a lubricant.
The ink composition preferably further includes an organic solvent, and the organic solvent preferably includes any of 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.
The coating composition is preferably a composition for being applied to a recording medium by a dipping method.

Furthermore, the present invention has the step of adhering the ink composition and the coating composition provided in the composition for inkjet printing according to the present invention onto a recording medium containing a fabric.

It is a flowchart which shows an example of the textile printing method of this embodiment.

Hereinafter, the embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as needed, but the present invention is not limited thereto, and the gist thereof Various modifications are possible without departing from the above. In the present specification, “(meth) acrylic resin” means both an acrylic resin and a corresponding methacrylic resin.

In the present specification, "printing" refers to recording (printing) ink on a recording medium including a fabric. Further, "ink jet printing" refers to recording (printing) an ink composition on a recording medium including a fabric using an ink jet method, and is a type of ink jet recording. The "printed matter" refers to one on which an ink composition is recorded on a recording medium containing a fabric to form an image.

[Composition set for ink jet printing]
A composition set for ink jet printing (hereinafter, also simply referred to as “composition set”) of the present embodiment is an ink composition containing a pigment, resin particles (hereinafter also referred to as first resin particles), and water. And a coating composition containing resin particles (hereinafter also referred to as second resin particles) and water. In addition, the first resin particle contains any of urethane resin, polycarbonate resin, (meth) acrylic resin, and styrene resin, and the content of the first resin particle is 1 part by mass of pigment (solid content). On the other hand, it is 1 to 5 parts by mass in solid content. Furthermore, the Young's modulus of the coating obtained by drying the ink composition is 1 to 25 MPa. Furthermore, the Young's modulus of the coating obtained by drying the coating composition is 50 MPa or less, and is higher than the Young's modulus of the coating obtained by drying the ink composition. The factors by which such a set of composition for ink jet printing can obtain a print having excellent feeling and fastness to rubbing are considered as follows. However, the factor is not limited to this. That is, when only the ink composition is used without using the conventional coating composition, the ink composition containing the pigment deposited on the recording medium is caused by the presence of the pigment on the surface of the ink composition. And the pigment on the surface is scraped off due to friction, etc., so that the rub fastness is not excellent. Further, the ink set containing the conventional pigment and the composition set provided with the coating composition substantially contain the pigment on the surface by depositing the ink composition and the coating composition in this order on the recording medium. Due to the presence of the coating composition which does not have a high viscosity, the fastness to rubbing is excellent. However, the conventional composition set using a coating composition having a high Young's modulus as a coating film is excellent in the fastness to rubbing, but not sufficiently good in the texture of the resulting printed matter. Moreover, although the conventional composition set at the time of using a coating composition with a low Young's modulus when it is set as a coating film is excellent in the feel, it is not sufficiently excellent in friction fastness. On the other hand, the composition set for ink jet printing of this embodiment mainly has a coat composition while the texture obtained with the printed matter obtained is excellent because the Young's modulus of the coating film obtained by drying the coat composition is 50 MPa or less. When the Young's modulus of the dried coating is higher than the Young's modulus of the coating obtained by drying the ink composition, the resulting printed matter is also excellent in the fastness to rubbing. Moreover, the composition set for inkjet printing of this embodiment is excellent also in discharge stability.

[Ink composition]
The ink composition of the present embodiment contains a pigment, resin particles, and water, and may further contain other necessary components as appropriate.

The Young's modulus of the coating obtained by drying the ink composition is 1 to 25 MPa, preferably 1 to 20 MPa, preferably 5 to 25 MPa, and more preferably 5 to 20 MPa. When the Young's modulus of a coating film is 25 MPa or less, it is excellent in the feel of the printed matter obtained. In addition, when the Young's modulus of the coating film is 1 MPa or more, a print having excellent fastness to rubbing can be obtained due to the fact that the adhesion to the fibers of the fabric as the recording medium is good. Also, the storage stability is excellent due to the good dispersibility of the ink composition. The Young's modulus of the coating film can be adjusted within the above range by appropriately adjusting the type and content of each component contained in the ink composition described later, particularly the type and content of the resin particles. . Moreover, the Young's modulus of a coating film is measured based on the method as described in an Example.

In the present specification, the coating film obtained by drying the ink composition means a film obtained by drying the ink composition. As a specific example of the coating film, a frame having a sufficient height to form a rectangular depression having an opening size of 3 × 19 cm is provided on a flat base material such as metal or glass, and the ink composition is provided in the frame Charge 10g of material. After drying overnight in the atmosphere, after heating at 160 ° C. and 15 minutes, the ink coating is obtained by peeling off the substrate. More specifically, it can be produced by the method described in the examples described later.

<Pigment>
The pigment of the present embodiment may be particles containing a pigment. Although it does not specifically limit as a pigment, For example, the following are mentioned.

The carbon black used for the black ink is not particularly limited, and examples thereof include Bonjetblack CW-1 (manufactured by Orient Chemical Industry Co., Ltd.), no. 2300, no. 900, MCF 88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200 B and the like (above, Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 and so on (above, Columbia Carbon), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (made by CABOT JAPAN K. K.), Color Black FW Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1 ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140 U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (above, Degussa (Degussa) company make) are mentioned.

The pigment used in the white ink is not particularly limited. I. Pigment white 6, 18, 21, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles and polymer particles.

The pigment used in the yellow ink is not particularly limited, and examples thereof include EMACOL SF Yellow J701F (trade name of Sanyo Dye Co., Ltd.), C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 154, 154, 154, 167, 172, 180 can be mentioned.

The pigment used in the magenta ink is not particularly limited. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 2, 48: 5, 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment Violet 19, 23, 32, 33, 36, 38, 43, 50.

The pigment used for the cyan ink is not particularly limited. I. Pigment blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60, and C.I. I. Direct Blue 199 is mentioned.

Further, pigments other than those described above are not particularly limited. I. Pigment green 7, 10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1,2,5,7,13,14,15,16,24,34,36,38,40,43,63.

The average particle size of the pigment is preferably 50 nm to 300 nm, more preferably 55 nm to 200 nm, still more preferably 60 nm to 150 nm, and still more preferably 65 nm to 100 nm. When the average particle diameter of the pigment particles is in the above range, the discharge stability tends to be more excellent, and a printed matter having better friction fastness can be obtained.

The average particle size in the present specification is based on volume unless otherwise specified. As a measurement method, for example, a zeta potential / particle size / molecular weight measurement system Zetasizer Nano ZS (manufactured by Malvern Co., Ltd.) is used, and a sample diluted with pure water having a solid content concentration of 0.1 mass% is measured at 25 ° C. The method to measure is mentioned.

The average particle size of the pigment particles can be adjusted, for example, by adjusting the stirring speed time of the step of dispersing the pigment, the amount and type of the dispersing agent, and the like. The average particle size of the pigment particles thus obtained may be measured and adjusted again based on the digit to obtain a desired dispersion. Alternatively, commercially available pigment particles having a known average particle diameter may be used. The average particle diameter of the pigment particles is not limited to the method described above, and may be adjusted by a method capable of adjusting.

In the ink composition, the content of the pigment is preferably 1.0 to 15% by mass, and more preferably 2.0 to 10% by mass in solid content with respect to the total amount (100% by mass) of the ink composition. More preferably, it is 3.0 to 7.0% by mass. When the content of the pigment particles is in the above range, the discharge stability tends to be more excellent.

<Resin particles>
The resin particles contained in the ink composition of the present embodiment are particles containing a resin (hereinafter, also referred to as “resin dispersion” or “resin emulsion”). Hereinafter, when describing and describing as "resin particle", without describing as "first resin particle" especially, it demonstrates with the description of the 2nd resin particle mentioned later.

The resin particles of the present embodiment may be self-dispersing resin particles (self-dispersing resin particles) into which a hydrophilic component necessary for stably dispersing in water is introduced (water can be obtained by using an external emulsifier) It may be resin particles that become dispersible. However, from the viewpoint of not inhibiting the reaction with the polyvalent metal compound that may be contained in the recording medium described later, the resin particles are preferably a self-emulsifying resin dispersion.

As the resin, for example, urethane resin, polycarbonate resin, (meth) acrylic resin (for example, Movinyl 6760 (trade name of Nippon Synthetic Chemical Co., Ltd.), acrylic resin), styrene resin, silicone resin, styrene acrylic Resin, fluorene resin, polyolefin resin, rosin modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and ethylene vinyl acetate resin Resin is mentioned. One of these resins may be used alone, or two or more thereof may be used in combination. Among these, the first resin particles preferably contain any one of a urethane resin, a polycarbonate resin, a (meth) acrylic resin, and a styrene resin, from the viewpoint of making the Young's modulus of the coating film suitable. More preferably, it contains a resin.

The urethane resin is a resin having a urethane bond in the molecule. From the viewpoint of the storage stability of the ink, and from the viewpoint of improving the reactivity with the pretreatment agent described later when the pretreatment agent contains a polyvalent metal compound, the urethane resin, such as a carboxy group, a sulfo group or a hydroxy group It is preferable that it is an anionic urethane type resin which has an anionic functional group.

As the urethane resin, in addition to the urethane bond, a polyether urethane resin having an ether bond in the main chain, a polyester urethane resin having an ester bond in the main chain, and a polycarbonate urethane resin having a carbonate bond in the main chain Can be mentioned. These urethane resins can be used in combination of multiple types. From the viewpoint of making relatively high the Young's modulus of the coating obtained by drying the ink composition and making the fastness to rubbing good, a urethane resin containing a carbonate bond in the main chain, that is, having a polycarbonate skeleton is preferable.

Commercially available urethane resins include ETERNACOLL UW-1501F, UW-5002 (all trade names of Ube Industries, Ltd.), Takelac WS-5000, W-6061, W-6110, WS-598, WS-5100 (above Mitsui Chemicals, Inc. trade name, Permarine UA-150, UA-200, Eu Coat UX-390 (all trade names of Sanyo Chemical Industries, Ltd.), Hydran WLS-210 (trade name of DIC Corporation).

The polycarbonate resin is a resin having a polycarbonate bond in the molecule. When a urethane resin is not used, it is preferable to use a polycarbonate resin instead.

Commercially available silicone resins include POLON-MF014, POLON-MF-18T, POLON-MF-33, KM-2002-T (trade names of Shin-Etsu Silicone Co., Ltd.), WACKER FINISH WR1100, NP2406, POWERSOFT FE 55 And TS 2406 (all trade names manufactured by Asahi Kasei Corporation).

It is preferable that the resin particle of this embodiment contains resin which has a crosslinkable group. When the resin having a crosslinkable group is contained, due to crosslinking between the resin particles, the rubbing fastness of the obtained printed matter tends to be more excellent. The crosslinkable group is not particularly limited as long as it can crosslink the resin particles, but it is preferable to contain either a blocked isocyanate group or a silanol group from the viewpoint of being superior to the fastness to rubbing (wetting) described later. The resin having such a crosslinkable group can be appropriately selected from the above-described resins in addition to those described in the examples to be described later.

The resin particles preferably contain 1.0% by mass or more and 5.0% by mass or less of the urethane resin, more preferably 1.5% by mass, with respect to 1.0 part by mass of the pigment particles contained in the above-described ink composition. It is contained by mass% or more and 4.2 mass% or less, more preferably 2.0 mass% or more and 3.5 mass% or less, still more preferably 2.5 mass% or more and 3.0 mass% or less. When the content of the urethane-based resin is in the above-mentioned range, a printed matter having more excellent rubbing fastness can be obtained.

The (meth) acrylic resin means a resin having a (meth) acrylic skeleton. The (meth) acrylic resin is not particularly limited, and examples thereof include polymers of (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic esters, and (meth) acrylic monomers. Copolymers of monomers and other monomers are included. Other monomers include vinyl monomers such as styrene. In the present specification, “(meth) acrylic” is a concept including both “methacrylic” and “acrylic”.

The average particle size of the resin particles is preferably 10 nm to 300 nm, more preferably 30 nm to 100 nm, and still more preferably 50 nm to 80 nm. When the average particle diameter of the resin particles is in the above range, the discharge stability tends to be more excellent, and a printed matter having better friction fastness can be obtained.

The average particle size of the resin particles can be measured by the same measurement method as that described for measuring the average particle size of the pigment particles.

The average particle diameter of the resin particles is, for example, the amount of monomers in the liquid phase at the time of synthesizing the resin, the reaction time, the stirring speed, the type and amount of the emulsifier to be present, and the stirring speed time of the step of dispersing the resin. It can adjust by adjusting the quantity of an emulsifier, etc. The average particle size of the resin particles thus obtained may be measured and adjusted again based on the result to obtain a desired dispersion. Alternatively, commercially available resin particles having a known average particle diameter may be used. Not limited to the above method, the average particle diameter of the resin particles may be adjusted by a method that can be adjusted.

The content of the first resin particles is 1 to 5 parts by mass in solid content, preferably 1.5 to 4.5 parts by mass, more preferably 2 parts by mass with respect to 1 part by mass (solid content) of the pigment. 4 parts by mass. When the content of the first resin particles is in the above range, a print having excellent discharge stability and excellent feeling and fastness to rubbing can be obtained.

The content of the first resin particles is preferably 5.0 to 20% by mass, and more preferably 7.0 to 15% by mass in solid content with respect to the total amount (100% by mass) of the ink composition. And more preferably 8.0 to 13% by mass, and still more preferably 9.0 to 10% by mass. When the content of the first resin particles is in the above range, it tends to be more excellent in discharge stability and storage stability, and it is possible to obtain a printed matter having better rub fastness.

<Water>
Examples of water according to the present embodiment include pure water such as ion exchange water, ultrafiltered water, reverse osmosis water, and distilled water, and those obtained by removing ionic impurities as much as possible, such as ultrapure water. . In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide or the like is used, it is possible to prevent the generation of mold and bacteria when storing the coagulation liquid for a long time. This tends to further improve storage stability.

<Organic solvent>
The ink composition of the present embodiment preferably further contains an organic solvent. The organic solvent is not particularly limited as long as it can be used together with water.

The type of organic solvent is not particularly limited, and examples thereof include cyclic nitrogen compounds, aprotic polar solvents, monoalcohols, alkyl polyols, and glycol ethers.

The aprotic polar solvent is not particularly limited, and examples thereof include cyclic ketone compounds, linear ketone compounds, and linear nitrogen compounds. Moreover, as cyclic nitrogen compounds and aprotic polar solvents, solvents of pyrrolidones, imidazolidinones, sulfoxides, lactones, amide ethers and imidazoles can be mentioned as a representative example. The pyrrolidones are not particularly limited as long as they have a pyrrolidone skeleton, and examples thereof include 2-pyrrolidone, N-alkyl-2-pyrrolidone and 1-alkyl-2-pyrrolidone. As imidazolidinones, for example, 1,3-dimethyl-2-imidazolidinone, as sulfoxides, for example, dimethyl sulfoxide, as lactones, for example, γ-butyrolactone, and as imidazoles, for example, imidazole, 1- Examples include methylimidazole, 2-methylimidazole, and 1,2-dimethylimidazole.

The monoalcohol is not particularly limited. For example, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pen Tanol, 3-pentanol, and tert-pentanol can be mentioned.

The alkyl polyol is not particularly limited. For example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propanediol), dipropylene glycol, trimethylolpropane, 1,3-propylene glycol (1 , 3-propanediol), isobutylene glycol (2-methyl-1,2-propanediol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4 -Diol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3- Hexanediol, 1,7-heptanediol, and 1,8-octane diol, and the like. Among them, the organic solvent in the ink composition preferably contains any of 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol from the viewpoint of obtaining excellent storage stability. . In a conventional ink composition containing resin particles and an organic solvent, when the Young's modulus of a coating film obtained by drying the ink composition is 1 to 25 MPa, the resin particles dissolve in the organic solvent, and the ink The composition may be thickened or generate foreign matter. On the other hand, in the ink composition of the present embodiment containing the resin particles and the organic solvent, even if the Young's modulus of the coating film obtained by drying the ink composition is 1 to 25 MPa, By containing any of diol, 1,4-butanediol and 1,5-pentanediol, the hydrophilicity becomes suitable, the resin particles become difficult to dissolve in the organic solvent, and the storage stability tends to be excellent.

The organic solvent is preferably water soluble. Water solubility means that water and an organic solvent are mixed and stirred at a mass ratio of 1: 1 at normal temperature, and then it can not be separated or confirmed to be cloudy.

Although it does not specifically limit as glycol ether, For example, glycol diethers and glycol monoethers are mentioned.

Specific examples of the glycol diether include, but are not limited to, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, tri Ethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetra ethylene glycol diethyl ether, tetra ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol Dimethyl ether, and, dipropylene glycol diethyl ether.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl 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 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 and the like.

As the organic solvent, one having an SP value of 25.0 to 35.0 is also preferably used, more preferably 26.0 to 34.0, and still more preferably 26.0 to 32.5. It is. When the SP value is in this range, the hydrophilicity of the ink composition is suitable, the resin particles become difficult to dissolve in the organic solvent, and the storage stability tends to be excellent.
Here, the “SP value” is referred to as “solubility parameter” and can also be referred to as “solubility parameter”. It means a value calculated using the Hansen equation shown below. The solubility parameter of Hansen is obtained by dividing the solubility parameter introduced by Hildebrand into three components, a dispersion term δd, a polar term δp, and a hydrogen bonding term δh, in a three-dimensional space. In the present specification, the SP value is represented by δ [(cal / cm ³ ) ^0.5 ], and a value calculated using the following formula is used.
δ [(cal / cm ³ ) ^0.5 ] = (δd ² + δp ² + δh ² ) ^0.5
Furthermore, δ d is preferably 13.0 to 20.0, and more preferably 14.0 to 17.2. The δp is preferably 10.0 to 17.0, and more preferably 10.5 to 15.0. δh is preferably 17.0 to 26.0, and more preferably 20.0 to 25.0. In such a case, the hydrophilicity of the ink composition is suitable, the resin particles become difficult to dissolve in the organic solvent, and the storage stability tends to be excellent.
Examples of the organic solvent for which the SP value and δd, δp, δh are suitable values as described above include 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol.

The content of the organic solvent is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 10% by mass with respect to the total amount (100% by mass) of the ink composition. It is 5% by mass. When the content of the organic solvent is in the above range, the drying property of the ink composition attached to the recording medium tends to be further improved, and a print having excellent rub fastness can be obtained. It is in.

<Lubricant>
The ink composition of the present embodiment preferably further contains a lubricant. By containing a lubricant, it is possible to obtain a print having more excellent in fastness to rubbing due to the lubricant coming into between fibers of the fabric contained in the recording medium (reduction in sticking feeling). is there.

Lubricants include, but are not limited to, calcium stearate, ammonium stearate, microcrystalline wax, polyethylene wax, paraffin wax, and polyethylene-paraffin wax. Moreover, as a commercial item, AQUACER 497 (made by BYK), Michem Emulsion 85250 (brand name made by Michelman) are mentioned, for example. Among these, polyethylene wax, polyethylene-paraffin wax, and polyethylene based compounds of Michem Emulsion 85250 (trade name of Michelman) are more preferable. One of these lubricants may be used alone, or two or more thereof may be used in combination.

In the ink composition, the content of the lubricant is preferably 0.1% by mass to 10% by mass, and more preferably 0.3% by mass to 5% by mass with respect to the total amount (100% by mass) of the ink composition. It is not more than 0% by mass, and more preferably not less than 0.5% by mass and not more than 2.0% by mass. When the content of the lubricant is in the above range, a printed matter having more excellent rubbing fastness can be obtained.

<Surfactant>
The ink composition preferably further contains a surfactant from the viewpoint of gloss. The surfactant is not particularly limited, and examples thereof include an acetylene glycol surfactant, a fluorine surfactant, and a silicone surfactant.

The acetylene glycol surfactant is not particularly limited, and 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5-decyne- An alkylene oxide adduct of 4,7-diol and an alkylene oxide adduct of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol The above is preferable. The commercial product of the acetylene glycol surfactant is not particularly limited, and, for example, E series (trade name of Air Products Japan, Inc.) such as Olfin (registered trademark) 104 series or Olfin E1010, Surfynol (registered trademark) 104, 465, 61, DF110D (trade name of Nissin Chemical Industry CO., Ltd.). The acetylene glycol surfactant may be used alone or in combination of two or more.

The fluorine-based surfactant is not particularly limited, and examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and the like. Perfluoroalkylamine oxide compounds can be mentioned. Commercially available fluorosurfactants are not particularly limited. For example, S-144, S-145 (all trade names, manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Florard-FC 4430 (all products Name, Sumitomo 3M Co., Ltd.); FSO, FSO-100, FSN, FSN-100, FS-300 (trade names, made by Dupont); FT-250, 251 (trade names, made by Neos, Inc.) It can be mentioned. The fluorinated surfactants may be used alone or in combination of two or more.

Although it does not specifically limit as a silicone type surfactant, For example, a polysiloxane type compound and polyether modified | denatured organosiloxane are mentioned. The commercial product of the silicone surfactant is not particularly limited. Specifically, SAG 503A (trade name, manufactured by Nisshin Chemical Industry Co., Ltd.), BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (above trade name, manufactured by BIC Chemie Co., Ltd.), 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 (trade names, Shin-Etsu And the like. The silicone surfactant may be used alone or in combination of two or more.

The content of the surfactant is preferably 0.05 to 2.5% by mass, more preferably 0.05 to 1.5% by mass, based on the total amount (100% by mass) of the ink composition. When the content of the surfactant is in the above range, the wettability of the ink composition attached to the recording medium tends to be further improved.

The ink composition includes, as other components, a softener, a wax, a solubilizer, a viscosity modifier, a pH adjuster such as triethanolamine, a moisturizer such as glycerin, an antioxidant, Proxel XL2 (a product manufactured by Arch Chemicals, Inc. Name) etc., various additives such as sodium chelating agent (eg ethylenediaminetetraacetic acid sodium acetate) for capturing metal ions that affect dispersion It can also be contained. Among the above, organic solvents such as glycerin are also included in the above-mentioned organic solvents.

[Coat composition]
The coating composition of the present embodiment contains resin particles and water, and can contain the components that can be contained in the above-described ink composition in the same manner as the ink composition. It can be further contained. However, the coating composition does not substantially contain a pigment from the viewpoint of securing excellent rubbing fastness. "Substantially free" means that the coating composition does not contain any pigment or that the content of the pigment is less than 0.1 mass with respect to the total amount (100% by mass) of the coating composition. means. Here, the resin particles contained in the coating composition are also referred to as second resin particles.

The Young's modulus of the coating obtained by drying the coating composition is 50 MPa or less and is higher than the Young's modulus of the coating obtained by drying the ink composition. When the Young's modulus of the coating film obtained by drying the coating composition is such a Young's modulus, it is possible to obtain a print having excellent feeling and fastness to rubbing.

The Young's modulus of the coating film obtained by drying the coating composition is preferably 5 to 50 MPa, more preferably 10 to 40 MPa, and still more preferably 20 to 30 MPa. When the Young's modulus of the coating film is in the above-mentioned range, a printed matter having a more excellent feeling and fastness to rubbing can be obtained. The Young's modulus of the coating film can be adjusted within the above range by appropriately adjusting the type and content of each component contained in the coating composition, particularly the type and content of the resin particles. Moreover, the Young's modulus of a coating film is measured based on the method as described in an Example.

The Young's modulus of the coating obtained by drying the coating composition is preferably 1 to 50 MPa higher, more preferably 3 to 35 MPa higher, still more preferably 5 to 25 MPa higher than the Young's modulus of the coating obtained by drying the ink composition. . When the Young's modulus of the coating film obtained by drying the coating composition is in the above-mentioned range, a printed matter having a more excellent feeling and fastness to rubbing can be obtained.

In the present specification, a coating film obtained by drying a coating composition means a film obtained by drying the coating composition. As a specific example of the coating film, a frame having a sufficient height to form a rectangular depression having an opening size of 3 × 19 cm is provided on a flat base material such as metal or glass, and the ink composition is provided in the frame Charge 10g of material. After drying overnight in the atmosphere, after heating at 160 ° C. and 15 minutes, the coated film is obtained by peeling off the substrate. More specifically, it can be produced by the method described in the examples described later.

The coating composition is preferably a composition for being applied to a recording medium by an immersion method, as described in [Adhesion step] described later. As a result, the coating composition is applied not only to the surface to which the ink composition of the fabric as the recording medium adheres, but also to the other back surface, the slippage between the fibers is improved, and the texture of the printed matter tends to be excellent. .

As the second resin particle, one that is the same as that of the above-described resin particle may be used, but among the above-described resin particles, the silicone resin is preferable from the viewpoint of making the Young's modulus of the coating film suitable. Is preferred. On the other hand, from the viewpoint of obtaining a printed matter excellent in feeling and fastness to rubbing, it is preferable to include a urethane resin, more preferably to include a urethane resin having a polycarbonate skeleton, and further a printed matter having further excellent rubbing fastness. From the viewpoint of obtaining, it is more preferable to include a urethane resin having a crosslinkable group.

The content of the second resin particles is preferably 0.1 to 13% by mass, and more preferably 0.1 to 10% by mass in solid content with respect to the total amount (100% by mass) of the ink composition. More preferably, it is 0.5 to 7% by mass, and still more preferably 1.0 to 3% by mass. When the content of the second resin particles is 10% by mass or less, the texture and the fastness to rubbing of the resulting printed matter tend to be excellent, and the content of the second resin particles is 0.1% by mass or more Tends to be more excellent due to the rubbing fastness of the resulting printed matter.

The coat composition of the present embodiment preferably further contains a lubricant. The inclusion of the lubricant tends to make it possible to obtain a print having more excellent rub fastness due to the improvement of the slipperiness of the surface of the recording medium.

In the coating composition, the content of the lubricant is more preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.3% by mass or more, based on the total amount (100% by mass) of the ink composition. It is not more than 0% by mass, and more preferably not less than 0.5% by mass and not more than 2.0% by mass. When the content of the lubricant is in the above range, a printed matter having more excellent rubbing fastness can be obtained.

The composition set of the present embodiment is used in an ink jet printing method described below.

[Ink jet printing method]
The ink jet printing method of the present embodiment has a step (adhesion step) of adhering the ink composition and the coating composition provided in the composition set of the present embodiment onto a recording medium including a fabric. FIG. 1 is a flowchart showing an example of the textile printing method of the present embodiment. As shown in FIG. 1, the textile printing method of the present embodiment may further include the following heating step and washing step in addition to the above-mentioned adhesion step.

The above-mentioned ink jet printing method is a printing method in which the ink composition is loaded into an ink jet apparatus and used. The ink jet apparatus is not particularly limited, and examples thereof include a drop-on-demand ink jet apparatus. In this drop-on-demand type ink jet apparatus, an apparatus adopting an ink jet textile printing method using a piezoelectric element provided in a head, and an ink jet using heat energy by a heater or the like of a heating resistance element provided in the head. There is an apparatus or the like that employs a textile printing method, and any of the inkjet textile printing methods may be adopted. Hereinafter, each process which the inkjet textile printing method has is demonstrated in detail.

[Attachment process]
In the adhesion step of the present embodiment, for example, the ink composition is discharged by an ink jet method toward the surface (image forming area) of the fabric which is a recording medium, and is adhered to the recording medium to form an image. The ejection conditions may be appropriately determined according to the physical properties of the ink composition to be ejected. Further, in the adhesion step of the present embodiment, for example, the coating composition is applied to the recording medium by an immersion method. Specifically, the coating composition is adhered by immersing the surface of the fabric, which is the recording medium to which the ink composition is adhered, in the coating composition. Here, when the coating composition is to be attached to the recording medium, it may be ejected and attached by an inkjet method as in the case of the ink composition. In the case where the coating composition is ejected by an inkjet method to adhere, it is preferable to adhere after the ink composition is attached.

[Heating process]
The printing method of the present embodiment may further include a heating step of heating the recording medium to which the ink composition and the coating composition are attached after the attaching step. By having the heating step, it is possible to better dye the dye on the fibers constituting the fabric. Although it does not specifically limit as a heating method, For example, HT method (high temperature steaming method), HP method (high pressure steaming method), thermosol method is mentioned.

Further, in the heating step, the surface on which the ink composition and the coating composition are to be attached on the recording medium may be subjected to pressure treatment or may not be subjected to pressure treatment. As a heating method which does not pressure-process the ink composition and the coating composition adhesion surface on the recording medium, oven drying (a method which does not press a conveyor oven, batch oven, etc.) can be mentioned. By having such a heating process, recorded matter productivity is further improved. Further, the heating method for applying pressure treatment to the ink composition and the coating composition adhesion surface on the recording medium is not particularly limited, and examples thereof include heat press and wet on dry. "Pressing" refers to applying pressure to the recording medium by bringing the individual into contact.

The temperature at the time of heat treatment is preferably 130 ° C. or more and 180 ° C. or less, more preferably 140 ° C. or more and 175 ° C. or less, and still more preferably 150 ° C. or more and 170 ° C. or less. When the temperature at the time of the heat treatment is in the above-mentioned range, it tends to be possible to better dye the dye on the fibers constituting the fabric.

[Washing process]
The printing method of the present embodiment may further include a cleaning step of cleaning the recording medium to which the ink composition and the coating composition have been adhered after the heating step. The washing step can effectively remove the pigment not dyed to the fibers. The washing step can be performed using, for example, water, and may be subjected to a soaping treatment as necessary. The soaping method is not particularly limited, but for example, a method of washing off the unfixed pigment with a hot soap solution or the like can be mentioned.

In this manner, recorded matter such as a print on which an image derived from the above ink composition is formed on a recording medium containing a fabric can be obtained.

<Recording medium>
As the recording medium of the present embodiment, any medium including a cloth (including the cloth itself) may be used. Examples of the fabric include, but are not limited to, natural fibers such as silk, cotton, wool, nylon, polyester, rayon and synthetic fibers. The cloth may be made of one kind of fiber or a mixture of two or more kinds of fibers. Among them, the effect of the present embodiment tends to be more easily obtained by using a blend of fibers having different permeability. As the fabric, any of the above-mentioned fibers may be used in any form such as woven fabric, knitted fabric, non-woven fabric and the like.

Hereinafter, the present invention will be more specifically described using examples. The present invention is not limited at all by the following examples.

[Material for Ink Composition and Coating Composition]
The main materials for the ink composition and the coating composition used in the production of the following recorded matter are as follows.
[Pigment dispersion]
C. I. Pigment blue 15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd., indicated as "PB-15: 3" in the table)
[Resin particles]
UW-1501F (ETERNACOLL UW-1501F manufactured by Ube Industries, Ltd., containing urethane resin and polycarbonate skeleton)
WS-598 (Mitsui Chemical's Takelac WS-598, urethane resin, containing polyester skeleton)
WS-5000 (Mitsui Chemical Co., Ltd. brand name Takelac WS-5000, urethane resin, containing polyester skeleton)
WS-5100 (Mitsui Chemical Co., Ltd. trade name Takelac WS-5100, urethane resin, containing polycarbonate skeleton)
UA-150 (trade name Permarine UA-150, manufactured by Sanyo Chemical Industries, containing urethane resin and polyether skeleton)
UA-200 (trade name Permarine UA-200 manufactured by Sanyo Chemical Industries, containing urethane resin and polyether skeleton)
UX-390 (trade name U-coat UX-390, manufactured by Sanyo Chemical Industries, Ltd., urethane resin)
WLS-210 (trade name Hydran WLS-210 manufactured by DIC, containing urethane resin and polycarbonate skeleton)
6760 (Nippon Synthetic Chemical Co., Ltd. trade name Movinyl 6760, acrylic resin)
POLON-MF014 (Shin-Etsu Silicone Co., Ltd., silicone resin)
POLON-MF-18T (Shin-Etsu Silicone Co., Ltd., silicone resin)
POLON-MF-33 (Shin-Etsu Silicone Co., Ltd., silicone resin)
KM-2002-T (Shin-Etsu Silicone Co., Ltd., silicone resin)
WACKER FINISH WR1100 (Asahi Kasei Co., Ltd. trade name, silicone resin)
NP2406 (manufactured by Asahi Kasei Corporation, silicone resin)
POWERSOFT FE 55 (manufactured by Asahi Kasei Corporation, silicone resin)
TS2406 (manufactured by Asahi Kasei Corporation, silicone resin)
〔Organic solvent〕
1,3-propanediol 1,4-butanediol 1,5-pentanediol propylene glycol ethylene glycol [lubricant]
AQUACER 497 (manufactured by BYK, paraffin wax)
[Other ingredients]
Glycerin SAG 503A (trade name of Nisshin Chemical Industry Co., Ltd., surfactant)
TEA (Triethanolamine, pH adjuster)
Proxel XL2 (brand name made by Arch Chemicals, preservative)
Pure water Dipropylene glycol monomethyl ether 3-butoxy-N, N-dimethylpropionamide 3-methoxy-N, N-dimethylpropionamide N-methylpyrrolidone triethylene glycol monobutyl ether [surfactant]
BYK 348 (trade name, made by Big Chemie)
MF 410 (trade name, manufactured by DIC, perfluoroalkyl group-containing carboxylate surfactant)
DW 800 (trade name, manufactured by Big Chemie, polyoxyethylene alkyl ether group-containing surfactant)
〔water〕
Pure water (ion-exchanged water)

[Preparation of Ink Composition]
Each material was mixed according to the composition shown in Table 1, Table 3 and Table 5 below to prepare an ink composition. Specifically, after mixing an organic solvent, a moisturizing agent, a pH adjuster, a surfactant, and a preservative with pure water, stirring is continued for 15 minutes, and then resin particles are dropped while being stirred little by little. The mixture was stirred for 1 hour to prepare a resin dispersion. Next, the prepared resin dispersion was dropped little by little into the pigment dispersion, and the mixture was stirred for 1 hour and filtered through an MF-membrane filter (SCWP: cellulose mixed ester, 8 μm) to prepare an ink composition.

[Preparation of Coating Composition]
Each material was mixed by the composition shown in the following Table 2, Table 4, and Table 5, and it fully stirred, and obtained the coating composition.

[Preparation of coating film sample]
A frame is made of silicon rubber (thickness: 5 mm) on a flat plate of stainless steel (SUS), and 10 g of each ink composition or each coating composition prepared above is charged into an opening 3 cm × 19 cm, Let dry overnight. Then, it heat-processed at 160 degreeC for 15 minutes, and obtained the coating film on SUS. Furthermore, the coating was peeled off from above SUS to obtain a coating.

〔Young's modulus〕
Using the TENSILON Universal Testing Machine (trade name: RTG-1250, manufactured by A & D Co., Ltd.), the obtained coating film was used under the conditions of a test specimen size width 10 mm, height 30 mm, and tensile speed 100 mm / min. The stress-strain curve was measured. Young's modulus [MPa] was determined by linear regression between the strain of 0.05 to 0.25% of the stress-strain curve. In addition, the film thickness of the coating film required for this measurement was calculated | required from actual measurement by a micrometer (Mittoyo product brand name "MDH-25M"). The Young's modulus of the coating obtained by drying each ink composition and the coating composition is shown in Tables 1 to 5.

[Production of textiles]
(Examples 1 to 21 and Comparative Examples 1 to 8)
An inkjet method using a modified machine of an inkjet printer (product name "PX-G930" manufactured by Seiko Epson Corporation) (having a means for fixing a fabric so as to enable recording on a fabric) to cotton broad (fabric). The respective ink compositions prepared above were deposited by As recording conditions, recording was performed under conditions of 23 to 24 ng / dot and 720 × 720 dpi. Thus, ink jet printing was performed.

Then, after drying in a draft for one night, heat treatment is carried out at 160 ° C. (dry) for 3 minutes using a high-temperature steamer HT-3-550 (manufactured by SAKURAI SEIKI INDUSTRY CO., LTD.), And the ink composition Were fixed on the recording medium to obtain a printed fabric. The imprinted fabric was then dipped into the coating composition in a 25 ° C. environment. Here, as the coating composition, the same coating composition as that of the ink composition was used in combination with the example number. After that, squeeze with a pick-up rate of 80% with a mangle, heat treatment is carried out for 5 minutes at 150 ° C. (dry) using a high-temperature steamer HT-3-550 (trade name made by SAKURAI SEIKI INDUSTRY CO., LTD.) The prints of Examples 1 to 21 and Comparative Examples 1 to 8 in which an image was formed on the medium (the ink was printed) were produced.

[Production of textiles]
(Examples 22 to 29)
The ink composition and the coating composition prepared above were ejected from different nozzle rows and adhered to a cotton broad (fabric) by the inkjet method using the above-mentioned inkjet printer remodeling machine. Here, as the ink composition and the coating composition, the ink composition and the coating composition having the same example number were used. As recording conditions, recording was performed under conditions of 23 to 24 ng / dot and 720 × 720 dpi. Also, during recording, both the ink composition and the coating composition were ejected while the carriage scanned once. The formed recording material had a portion in which the dots formed by the ink composition and the dots formed by the coating composition overlapped. Thus, ink jet printing was performed.

Then, after drying in a draft for one night, heat treatment is carried out at 160 ° C. (dry) for 3 minutes using a high-temperature steamer HT-3-550 (manufactured by Izu Dye Industry Co., Ltd.), and the ink composition And the coating composition was fixed on the recording medium to produce the prints of Examples 22 to 29 in which an image was formed (the ink was printed) on the recording medium.

[Texture]
Each printed material obtained in the above-mentioned [Production of printed material] is cut into a size of 20 × 20 cm, and a tensile shear tester KES-FB1-A (trade name of Kato Tech Co., Ltd.) is used, 10 gf / cm The tension-curvature curve was measured under the conditions of shear tension of ± 8 ° shear angle. Shear hardness [gf / (cm · deg)] was determined by linear regression between the measured 0.5 ° to 2.5 ° of the tension-curvature curve. Furthermore, with respect to cotton broads to which the ink composition and the coating composition were not applied, shear hardness was determined in the same manner as the above-mentioned printed matter. The absolute value of the difference between the shear hardness of the print and the shear hardness of cotton broad was calculated, and the texture was evaluated according to the following evaluation criteria. When the evaluation result is 3 to 5, it can be said that the touch is particularly good and the effect of the present invention is obtained.
(Evaluation criteria)
5: The absolute value of the difference in shear hardness is 0.5 or less.
4: The absolute value of the difference in shear hardness is more than 0.5 and not more than 1.0.
3: The absolute value of the difference in shear hardness is more than 1.0 and not more than 1.5.
2: The absolute value of the difference in shear hardness is greater than 1.5 and less than 2.0.
1: The absolute value of the difference in shear hardness is more than 2.0.

[Rubbing fastness (drying)]
For each printed material obtained in the above-mentioned [Production of printed material], using a Gakushin type friction fastness tester AB-301 (trade name made by Tester Sangyo Co., Ltd.), load of friction element shape 45R, 200 gf, reciprocating distance 100 cycles of reciprocation are performed under conditions of speed of 20 cm and 10 cm / s, and then dye transfer is performed using a white cloth for JIS color fastness test (JIS L 0803-based 3-1, gold width 3) The concentration OD value was measured using a Gretag Macbeth Spectroscan (D65 light source, reflection angle 2 °), and the fastness to rubbing was evaluated according to the following evaluation criteria. The lower the dye transfer density OD value, the better the rub fastness. When the evaluation result is 3 to 5, it can be said that the effect of the present invention is obtained.
(Evaluation criteria)
6: The dye transfer density OD value is 0.10 or less.
5: The dye transfer density OD value is greater than 0.10 and less than or equal to 0.15.
4: The dye transfer density OD value is more than 0.15 and 0.20 or less.
3: The dye transfer density OD value is more than 0.20 and less than 0.25.
2: The dye transfer density OD value is more than 0.25 and 0.30 or less.
1: The dye transfer density OD value is over 0.30.

[Rubbing fastness (wet)]
The evaluation is the same as in the above evaluation of the above [Rubbing fastness (drying)] except that the white cloth for the JIS color fastness test is replaced by one impregnated with the same amount of water as the white cloth for the JIS color fastness test. The dye transfer density OD value was measured, and the fastness to rubbing was evaluated according to the following evaluation criteria. When the evaluation result is 3 to 5, it can be said that the effect of the present invention is obtained.
(Evaluation criteria)
5: The dye transfer density OD value is 0.15 or less.
4: The dye transfer density OD value is more than 0.15 and 0.20 or less.
3: The dye transfer density OD value is more than 0.20 and less than 0.25.
2: The dye transfer density OD value is more than 0.25 and 0.30 or less.
1: The dye transfer density OD value is over 0.30.

[Discharge stability]
Each of the prepared ink compositions is filled in an ink cartridge of an ink jet printer (product name "PX-G930" manufactured by Seiko Epson Corporation), and the ink composition is manufactured by an ink jet discharge observation apparatus "Dot View" (trade name manufactured by Tritech Co., Ltd.) The discharge speed of the material was adjusted to the values shown below, the nozzle slippage and the flight curve were observed, and the discharge stability was evaluated according to the following evaluation criteria.
(Evaluation criteria)
3: A nozzle having a nozzle missing and a flying curve at a discharge speed of 6 m / s can not be confirmed.
2: The number of nozzles causing nozzle missing and flying deflection at a discharge speed of 6 m / s is more than 0% and 3% or less with respect to the total number of nozzles.
1: The number of nozzles causing nozzle missing and flying deflection at an ejection speed of 6 m / s is more than 3% with respect to the total number of nozzles.

〔Evaluation results〕
A composition set for ink jet printing comprising an ink composition containing a pigment, a first resin particle and water, and a coating composition containing a second resin particle and water, wherein the first resin particle is The content of the first resin particles is any one of urethane resin, polycarbonate resin, (meth) acrylic resin and styrene resin, and the content of the first resin particle is 1 to 5 mass in solid content with respect to 1 mass part (solid content) of pigment Young's modulus of the coating obtained by drying the ink composition is 1 to 25 MPa, and Young's modulus of the coating obtained by drying the coating composition is 50 MPa or less, and the ink composition is dried. The composition set for ink jet printing of each example manufactured so as to be higher than the Young's modulus of the coated film has an evaluation result of texture, fastness to rubbing (drying) and fastness to rubbing (wetting) of “3 More than , It was found that is excellent.
In Comparative Example 1, when the Young's modulus in the ink composition is less than 1 MPa, the intermolecular interaction in the coating film is weakened and the adhesion of the coating film is reduced, and the coating film of the ink composition and the coating composition The friction at the interface with the coating film is likely to occur, or the strength of the coating film itself is reduced to cause breakage in the coating layer, friction It is presumed that the evaluation results of fastness (drying) and fastness to rubbing (wet) were “1”.
In Comparative Example 2, when the Young's modulus in the ink composition is the same as the Young's modulus in the coating composition, the intermolecular interaction in the coating film is intensified and the coating film shrinks, and the coating film and the coating of the ink composition Friction fastness (drying) and due to the tendency of stress rupture at the interface of the composition with the coating film or the tendency of stress rupture of the recording medium (fiber) to occur It is inferred that the evaluation result of the fastness to rubbing (moisture) was “2”.

Claims (13)

An ink jet printing composition set comprising: an ink composition containing a pigment, resin particles and water; and a coating composition containing resin particles and water,
The resin particles contained in the ink composition include any of a urethane resin, a polycarbonate resin, a (meth) acrylic resin, and a styrene resin,
The content of the resin particles contained in the ink composition is 1 to 5 parts by mass in solid content with respect to 1 part by mass of the pigment solid content,
The Young's modulus of the coating obtained by drying the ink composition is 1 to 25 MPa,
The Young's modulus of the coating obtained by drying the coating composition is 50 MPa or less, and is higher than the Young's modulus of the coating obtained by drying the ink composition.
Composition set for inkjet printing. The Young's modulus of the coating obtained by drying the ink composition is 1 to 20 MPa.
An ink jet printing composition set according to claim 1. The Young's modulus of the coating obtained by drying the ink composition is 5 to 20 MPa.
An ink jet printing composition set according to claim 1. The Young's modulus of the coating obtained by drying the coating composition is 5 to 25 MPa higher than the Young's modulus of the coating obtained by drying the ink composition.
The composition set for ink jet printing according to any one of claims 1 to 3. The Young's modulus of the coating obtained by drying the coating composition is 5 to 50 MPa.
An ink jet printing composition set according to any one of claims 1 to 4. The resin particles contained in the ink composition include a resin having a crosslinkable group,
The composition set for ink jet printing according to any one of claims 1 to 5. The crosslinkable group contains either a blocked isocyanate group or a silanol group,
The composition set for ink jet printing according to claim 6. The resin particles contained in the ink composition include a urethane resin having a polycarbonate skeleton,
A composition set for ink jet printing according to any one of claims 1 to 7. The content of the resin particles contained in the coating composition is 0.1 to 10% by mass in solid content with respect to the total amount of the coating composition.
A composition set for ink jet printing according to any one of claims 1 to 8. The ink composition or the coating composition further comprises a lubricant.
The composition set for ink jet printing according to any one of claims 1 to 9. The ink composition further comprises an organic solvent,
The organic solvent includes any of 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol.
The composition set for ink jet printing according to any one of claims 1 to 10. The coating composition is a composition to be applied to a recording medium by a dipping method.
A composition set for ink jet printing according to any one of claims 1 to 11. The ink composition and the coating composition provided in the composition for inkjet printing according to any one of claims 1 to 12 are deposited on a recording medium including a fabric.
Ink jet printing method.

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