JP2019131919A - Treatment liquid composition for inkjet pigment printing, treatment liquid composition set for inkjet pigment printing and inkjet pigment printing method - Google Patents

Abstract

To provide a treatment liquid composition for inkjet pigment printing that makes it possible to obtain printed matter having excellent color development, and a treatment liquid composition set for inkjet pigment printing and an inkjet pigment printing method.SOLUTION: A treatment liquid composition for inkjet pigment printing is used by attaching to a fabric in inkjet pigment printing, the treatment liquid composition containing a cationic compound, a nonionic fluorine-based surfactant, a resin particle, and water.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a treatment liquid composition for inkjet pigment printing, a treatment liquid composition set for inkjet pigment printing, and an inkjet pigment printing method.

  Fabrics and the like are dyed (printed) using an ink jet recording method. Conventionally, screen printing methods, roller printing methods, and the like have been used as recording methods for fabrics (woven fabrics and non-woven fabrics), but inkjet recording methods should be applied from the viewpoints of various small-scale productivity and immediate printability. Therefore, various studies have been made.

  In this textile ink jet recording method, a so-called ink jet pigment textile printing method (hereinafter simply referred to as “pigment textile printing”) in which a fabric is printed by blending an ink composition (hereinafter also simply referred to as “ink”) with a pigment and a fixing resin. Is also being studied. In this pigment textile printing, the color developability may be deteriorated when the ink penetrates into the inside of the fabric, and the improvement of the color developability is demanded. In particular, in a polyester or polyester blended fabric, it is difficult to obtain a good color because the ink easily sinks into the fabric.

  Therefore, for the purpose of improving the color developability of the obtained printed matter, it is known to use a treatment liquid such as a pretreatment agent in pigment printing to physically fix the pigment on the surface of the fabric fiber or the like (for example, , See Patent Document 1).

JP 2008-266853 A

  However, in the ink jet pigment printing method using the treatment liquid and the pigment printing ink jet ink composition, further improvement in color developability is required.

  Accordingly, some embodiments according to the present invention provide an inkjet pigment printing treatment liquid composition, an inkjet pigment printing treatment liquid composition set, and a print product excellent in color developability by solving the above-described problems. It is to provide an inkjet pigment printing method.

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

[Application Example 1]
One aspect of the treatment liquid composition for inkjet pigment printing according to the present invention is:
In inkjet pigment printing, a treatment liquid composition used by adhering to a fabric,
It contains a cationic compound, a nonionic fluorosurfactant, resin particles, and water.

According to the first application example, the nonionic fluorosurfactant adhering to the cloth retains the ink on the cloth surface, thereby suppressing the penetration of the ink into the cloth and the sinking of the pigment into the cloth. To do. Further, since the surfactant is nonionic, uneven color development is less likely to occur. Thus, according to the application example 1, when the treatment liquid composition for inkjet pigment printing that adheres to the fabric contains the nonionic fluorosurfactant, a printed matter having excellent color developability can be obtained.

[Application Example 2]
In the above application example,
The fabric can be made of polyester or polyester blended yarn.

  According to the application example 2, the coloring property can be obtained even in the pigment printing on the cloth made of polyester or the polyester blended yarn in which the ink easily sinks down due to the action of holding the ink by the nonionic fluorosurfactant on the cloth surface. An excellent printed product can be obtained.

[Application Example 3]
In the above application example,
The cationic compound may be a polyvalent metal salt, an organic acid, or a cationic resin.

  According to Application Example 3, when the cationic compound is a polyvalent metal salt or an organic acid, unevenness in color development hardly occurs, and a printed matter excellent in color developability can be obtained.

[Application Example 4]
In the above application example,
The cationic compound can contain either calcium nitrate or calcium chloride.

  According to the application example 4, when the cationic compound is either calcium nitrate or calcium chloride, unevenness in color development hardly occurs, and a printed matter excellent in color developability can be obtained.

[Application Example 5]
In the above application example,
The nonionic fluorosurfactant may have an HLB value in the range of 6 to 15.

  According to Application Example 5, when the HLB value of the nonionic fluorosurfactant is in the range of 6 or more and 15 or less, the permeation of the ink into the fabric is suppressed, and a printed matter with more excellent color developability is obtained. It is done.

[Application Example 6]
In the above application example,
The nonionic fluorosurfactant may have a polyoxyethylene group and a fluorinated alkyl group.

  According to Application Example 6, since the nonionic fluorosurfactant has a polyoxyethylene group which is a hydrophilic group and a fluorinated alkyl group which is a hydrophobic group, the penetration of the ink into the fabric is further suppressed. In this way, it is possible to suppress the sinking of the pigment into the fabric, and to obtain a printed matter with more excellent color development.

[Application Example 7]
In the above application example,
The resin particles may be nonionic or cationic resin particles.

  According to Application Example 7, since the resin particles are nonionic resin particles, a printed matter excellent in color development and friction fastness can be obtained particularly in printing on cotton. Further, according to Application Example 7, when the resin particles are cationic resin particles, a printed matter excellent in color development and friction fastness can be obtained particularly in printing on a fabric composed of polyester or polyester blended yarn. It is done.

[Application Example 8]
One aspect of the set for inkjet pigment printing according to the present invention is:
A treatment liquid composition for inkjet pigment printing according to any one of Application Examples 1 to 7,
A pigment printing inkjet ink composition containing a pigment, resin particles, and water.

  According to the application example 8, a printed matter having excellent color developability can be obtained. In particular, the pigment printing using the ink containing the chromatic pigment is further performed on the pigment printing using the pigment printing inkjet ink composition. In two-layer printing, it is possible to provide a pigment-printed inkjet ink composition set that provides a printed product with excellent color developability.

[Application Example 9]
In the above application example,
The resin particles contained in the pigment printing inkjet ink composition may contain a polycarbonate urethane resin.

  According to Application Example 9, when a nonionic fluorosurfactant is used, the printed matter obtained tends to be inferior in fastness, but by using polycarbonate urethane resin particles as the resin particles, the pigment becomes the surface of the fabric. Even when a nonionic fluorosurfactant is used, a printed matter excellent in color development and friction fastness can be obtained.

[Application Example 10]
In the above application example,
The pigment textile printing inkjet ink composition may further contain a fluorine-based surfactant.

  According to the application example 10, since the pigment printing inkjet ink composition further contains a fluorine-based surfactant, the permeability of the ink into the fabric is further controlled, so that a printed product with excellent color development can be obtained. It is done.

[Application Example 11]
One aspect of the inkjet pigment printing method according to the present invention is:
A step of depositing the pigment-printed inkjet ink composition by an inkjet method in a region to which the inkjet pigment printing treatment liquid composition described in any one of Application Examples 1 to 7 is adhered;

  According to Application Example 11, since the pigment-printed inkjet ink composition is adhered onto the inkjet pigment printing treatment liquid composition of the above-described application example, the penetration of the ink into the fabric is suppressed. Further, the ink component aggregates due to the reaction or interaction between the cationic compound of the ink jet pigment printing treatment liquid composition and the ink component. As a result, a printed material having excellent color developability can be obtained.

1 is a schematic perspective view of a printing apparatus that performs an inkjet pigment printing method according to the present embodiment.

  Several embodiments of the present invention will be described below. Embodiment described below demonstrates an example of this invention. The present invention is not limited to the following embodiments, and includes various modifications that are implemented without departing from the scope of the present invention. Note that not all of the configurations described below are essential configurations of the present invention.

  Hereinafter, regarding the treatment liquid composition for inkjet pigment printing, the treatment liquid composition set for inkjet pigment printing, and the inkjet pigment printing method according to the present embodiment, the configuration of a printing apparatus capable of performing this, the treatment liquid composition for inkjet pigment printing In addition, a pigment printing inkjet ink composition (hereinafter referred to as “pigment printing ink”) that constitutes a processing liquid composition set for inkjet pigment printing (hereinafter also referred to as “processing liquid set”), which includes a processing liquid composition for inkjet pigment printing. "Ink composition", also referred to as "ink"), inkjet pigment printing treatment liquid composition (hereinafter also referred to as "treatment liquid"), inkjet pigment printing treatment liquid composition set, and inkjet pigment printing method The fabric and the inkjet pigment printing method will be described in detail in this order.

1. First, an example of a printing apparatus used in this embodiment will be described with reference to the drawings. In addition, the textile printing apparatus used by this embodiment is not limited to the following aspects.

  The textile printing apparatus used in the present embodiment will be described by taking an on-carriage type printer in which an ink cartridge is mounted on a carriage as an example. However, the textile printing apparatus is limited to an on-carriage type printer. Instead, the printer may be an off-carriage type printer in which the ink cartridge is not mounted on the carriage and is fixed to the outside.

  The printer used in the following description is a serial printer in which a print head is mounted on a carriage that moves in a predetermined direction, and droplets are ejected onto a recording medium when the head moves as the carriage moves. However, the textile printing apparatus used in the present invention is not limited to a serial printer, the head is formed wider than the width of the recording medium, and the print head ejects droplets onto the recording medium without moving. A line printer may be used.

  In each drawing used for the following description, the scale of each member is appropriately changed in order to make each member a recognizable size.

Examples of the textile printing apparatus include an ink jet printer (hereinafter also referred to as “printer”) on which the ink jet head shown in FIG. 1 is mounted. As shown in FIG. 1, the printer 1 has a carriage 4 on which an inkjet head 2 is mounted and an ink cartridge 3 is detachably mounted, and a fabric M that is disposed below the inkjet head 2 and is a recording medium is conveyed. A platen 5, a heating mechanism 6 for heating the fabric M, a carriage moving mechanism 7 for moving the carriage 4 in the medium width direction of the fabric M, and a medium feeding mechanism 8 for conveying the fabric M in the medium feeding direction. I have it. The printer 1 also has a control device CONT that controls the operation of the entire printer 1. The medium width direction is the main scanning direction (head scanning direction). The medium feeding direction is a sub-scanning direction (a direction orthogonal to the main scanning direction).

  The inkjet head 2 is means for attaching ink to the fabric M, and includes a plurality of nozzles (not shown) for ejecting ink on a surface facing the fabric M to which ink is attached. The plurality of nozzles are arranged in a row, thereby forming a nozzle surface on the surface of the nozzle plate.

  As a method for ejecting ink from the nozzle, for example, a strong electric field is applied between the nozzle and the acceleration electrode placed in front of the nozzle, and droplet-like ink is continuously ejected from the nozzle, so that the ink droplets are discharged. A method that discharges in response to the recorded information signal while flying between the deflection electrodes (electrostatic suction method); by applying pressure to the processing liquid with a small pump and mechanically vibrating the nozzle with a quartz resonator, A method for forcibly ejecting ink droplets; a method in which pressure and recording information signals are simultaneously applied to ink by a piezoelectric element, and ink droplets are ejected and recorded (piezo method); a microelectrode according to recording information signals And a method (thermal jet method) in which the ink is heated and foamed to discharge and record ink droplets.

  As the ink jet head 2, either a line ink jet head or a serial ink jet head can be used. In this embodiment, a serial ink jet head is used.

  Here, the textile printing apparatus provided with the serial type ink jet head performs recording by performing scanning (pass) for discharging ink while moving the ink jet head for recording relative to the recording medium a plurality of times. Is. As a specific example of a serial type inkjet head, an inkjet head is mounted on a carriage that moves in the width direction of the recording medium (a direction that intersects the conveyance direction of the recording medium), and the inkjet head moves as the carriage moves. By doing so, there are those that discharge droplets onto a recording medium.

  On the other hand, a textile printing apparatus provided with a line type ink jet head performs recording by performing a scan (pass) for ejecting ink once while moving the ink jet head relative to a recording medium. As a specific example of the line-type ink jet head, there is an ink jet head in which the ink jet head is formed wider than the width of the recording medium and droplets are ejected onto the recording medium without moving the ink jet head.

  The ink cartridge 3 that supplies ink to the inkjet head 2 is composed of four independent cartridges. For example, different types of ink are filled in each of the four cartridges. The ink cartridge 3 is detachably attached to the inkjet head 2. In the example of FIG. 1, the number of cartridges is four. However, the number of cartridges is not limited to this, and a desired number of cartridges can be mounted.

  The carriage 4 is attached in a state of being supported by a guide rod 9 which is a support member installed in the main scanning direction. The carriage 4 is moved in the main scanning direction along the guide rod 9 by the carriage moving mechanism 7. In the example of FIG. 1, the carriage 4 moves in the main scanning direction. However, the present invention is not limited to this, and the carriage 4 may move in the sub scanning direction in addition to the movement in the main scanning direction. .

  As long as the heating mechanism 6 is provided at a position where the fabric M can be heated, the installation position is not particularly limited. In the example of FIG. 1, the heating mechanism 6 is installed on the platen 5 at a position facing the inkjet head 2. As described above, when the heating mechanism 6 is installed at a position facing the inkjet head 2, the adhesion position of the droplet on the fabric M can be surely heated, so that the droplet adhered to the fabric M can be efficiently dried. .

  For the heating mechanism 6, for example, a print heater mechanism that heats the fabric M in contact with a heat source, a mechanism that irradiates infrared rays or microwaves (electromagnetic waves having a maximum wavelength of about 2,450 MHz), or hot air is blown. For example, a dryer mechanism can be used.

  The heating of the fabric M by the heating mechanism 6 is performed before or when the droplets discharged from the nozzles of the inkjet head 2 adhere to the fabric M. Control of various heating conditions (for example, heating timing, heating temperature, heating time, etc.) is performed by the control device CONT.

  The heating of the fabric M by the heating mechanism 6 is performed so that the fabric M maintains a temperature range of 35 ° C. or more and 65 ° C. or less from the viewpoints of wetting and spreading of ink, improvement of permeability and drying property, ejection stability, and the like. . Here, the temperature at which the fabric M is heated means the temperature of the recording surface of the fabric M during heating.

  The printer 1 may further have a second heating mechanism (not shown) in addition to the heating mechanism 6. In that case, the second heating mechanism is installed downstream of the heating mechanism 6 in the conveyance direction of the fabric M. The second heating mechanism heats the fabric M after the fabric M is heated by the heating mechanism 6, that is, after the droplets discharged from the nozzles adhere to the fabric M. Thereby, the drying property of the ink droplets adhering to the fabric M is improved. Any mechanism described in the heating mechanism 6 (for example, a dryer mechanism, a heat press machine, or the like) can be used as the second heating mechanism. Heating by the second heating mechanism is preferably performed so that the fabric M maintains a temperature range of 100 ° C. or higher and 200 ° C. or lower.

  The linear encoder 10 detects the position of the carriage 4 in the main scanning direction with a signal. This detected signal is transmitted to the control device CONT as position information. The control device CONT recognizes the scanning position of the recording head 2 based on the position information from the linear encoder 10, and controls the recording operation (discharge operation) by the recording head 2. Further, the control device CONT is configured to be able to variably control the moving speed of the carriage 4.

2. Pigment-printed inkjet ink composition The pigment-printed inkjet ink composition used in the present embodiment contains a pigment, resin particles, a nonionic fluorosurfactant, and water, and is used by adhering to a fabric. It is characterized by. Hereinafter, the pigment printing inkjet ink composition will be described.

  In addition, the pigment printing inkjet ink composition used in this embodiment may constitute an inkjet pigment printing set together with the inkjet pigment printing treatment liquid composition according to this embodiment described later. When the pigment printing inkjet ink composition set used in this embodiment includes a plurality of pigment printing inkjet ink compositions, one of them is a white pigment printing inkjet ink composition containing a white pigment as a pigment. Other than that, a chromatic color pigment printing inkjet ink composition containing a chromatic color pigment is preferable. In this case, it is possible to perform two-layer printing in which color printing is performed on a white background in the inkjet pigment printing method described later.

2.1. Pigment The pigment-printed inkjet ink composition used in the present embodiment contains a pigment. When the pigment is attached to the fabric, the fabric is printed and a printed product (printed product) is formed.

  As the pigment, both organic pigments and inorganic pigments can be used, and pigments of any color can be used. In the case of a set including a plurality of pigment-printed inkjet ink compositions, one of them preferably includes a white pigment as the pigment, and the other preferably includes a chromatic pigment.

  Examples of the white pigment include, but are not limited to, white inorganic pigments such as titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. In addition to the white inorganic pigment, white organic pigments such as white hollow resin particles and polymer particles can also be used.

  The color index (CI) of the white pigment is not limited to the following, but for example, C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium mica), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (gypsum) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate), and the like. Among these, titanium oxide is preferable as the white pigment because it is excellent in color developability, concealability, and visibility (brightness), and a good dispersed particle diameter can be obtained.

  Among the titanium oxides, rutile type titanium oxide, which is a general white pigment, is preferable. This rutile type titanium oxide may be produced by itself or may be commercially available. As an industrial production method for producing rutile-type titanium oxide (in powder form) by itself, conventionally known sulfuric acid method and chlorine method can be mentioned. Examples of commercially available rutile titanium oxide include Tipaque (registered trademark) CR-60-2, CR-67, R-980, R-780, R-850, R-980, R-630, R- 670, PF-736, etc. (all are trade names, manufactured by Ishihara Sangyo Co., Ltd.).

  Examples of the chromatic color pigment include pigments other than the above white pigment. Examples of the pigment other than the white pigment include, but are not limited to, organic pigments such as azo, phthalocyanine, dye, condensed polycyclic, nitro, and nitroso (brilliant carmine 6B, lake red C, and watching). Red, disazo yellow, hansa yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.), metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese and nickel, metal oxides And sulfides, carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black (CI pigment black 7), and inorganic pigments such as ocher, ultramarine, and bitumen can be used. .

More specifically, as carbon black used as a black pigment, 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical Co., Ltd.), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. , Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (above, manufactured by Cabot), Color Black FW1, Col Black FW2, Col Black FW2, Col Black FW2, Col Black FW2, Col Black FW Black FW200, Color B1ack 150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V,
Examples include Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa).

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 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, 153, 154, 167, 172, 180 and the like.

  Examples of magenta pigments include C.I. 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 (Ca), 48 (Mn), 57 (Ca), 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, and C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

  Examples of cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and C.I. I. Bat Blue 4, 60 and the like.

  Examples of pigments other than black, yellow, magenta, and cyan include C.I. I. Pigment green 7, 10, and C.I. I. Pigment brown 3, 5, 25, 26, and C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

  The pigments described above may be used alone or in combination of two or more.

  Although the content of the pigment contained in the pigment-printed inkjet ink composition used in the present embodiment varies depending on the pigment type used, the total mass (100% by mass) of the ink is ensured to ensure good color developability. On the other hand, it is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and further preferably 5% by mass or more and 13% by mass or less. In particular, when titanium oxide is used as a pigment contained in the ink, the content of titanium oxide is difficult to settle and has excellent concealability and color reproducibility on fabrics with low lightness. The content is preferably 3% by mass or more and 25% by mass or less, more preferably 5% by mass or more and 20% by mass or less. Further, it is preferably 7% by mass or more and 15% by mass or less, and more preferably 12% by mass or less.

  In preparing the pigment printing inkjet ink composition, a pigment dispersion in which a pigment is dispersed in advance may be prepared, and the obtained pigment dispersion may be added to and mixed with other material dispersions. As a method for obtaining such a pigment dispersion, a method is used in which a self-dispersing pigment is dispersed in a dispersant without using a dispersant, and a pigment is dispersed in a dispersant using a polymer dispersant (resin dispersant). And a method of dispersing the surface-treated pigment in a dispersant.

<Resin dispersant>
Among these, the resin dispersant is not particularly limited, but examples thereof include polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic ester copolymer, acrylic acid. -Acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene -Α-methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer , Vinyl acetate-maleic acid ester copolymer, vinyl acetate -A crotonic acid copolymer, a vinyl acetate-acrylic acid copolymer, etc., and these salts are mentioned. Among these, a copolymer of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and a polymer comprising a monomer having both a hydrophobic functional group and a hydrophilic functional group are particularly preferable. Moreover, as a form of a copolymer, any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.

  A commercial item can also be used as a resin dispersing agent. Specifically, Joncryl 67 (weight average molecular weight: 12500, acid value: 213), Joncryl 678 (weight average molecular weight: 8,500, acid value: 215), Joncryl 586 (weight average molecular weight: 4) , 600, acid value: 108), joncryl 611 (weight average molecular weight: 8,100, acid value: 53), joncryl 680 (weight average molecular weight: 4,900, acid value: 215), joncryl 682 (weight) Average molecular weight: 1,700, acid value: 238), Joncryl 683 (weight average molecular weight: 8,000, acid value: 160), Joncryl 690 (weight average molecular weight: 16,500, acid value: 240) (above Trade name, manufactured by BASF Japan Ltd.).

2.2. Resin Particles The pigment printing inkjet ink composition used in the present embodiment contains resin particles. By forming a resin film, the resin particles have a function of improving the fixability of an image formed by the ink composition, and can improve the fastness to washing and friction fastness of the image. As the resin particles, those in the emulsion state and in the solution state can be used, but from the viewpoint of suppressing the increase in the viscosity of the ink, it is preferable to use those in the emulsion state.

  Examples of the resin particles include acrylic resins, styrene acrylic resins, fluorene resins, urethane resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, Vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, and the like can be used. These resins may be used alone or in combination of two or more.

As the resin of the resin particles, among the above, it is preferable to use at least one selected from a urethane-based resin and an acrylic-based resin because it has a high degree of freedom in design and thus easily obtains desired physical properties. From the viewpoint of improving fastness, it is more preferable to use a urethane resin. The urethane resin may be any of a polyether type including an ether bond, a polyester type including an ester bond, a polycarbonate type including a carbonate bond, and the like. When the urethane-based resin having a crosslinkable group is crosslinked (crosslinked product), the elongation at break and 100% modulus can be adjusted by changing the density of the crosslinking points and the kind of the main chain. . Among these, the urethane-based resin having a crosslinkable group having a polycarbonate skeleton or a polyether skeleton has a good balance between elongation at break and 100% modulus, friction fastness of an image, A polycarbonate-based urethane resin having a polycarbonate-based skeleton is more preferable because it tends to improve the texture. In particular, since the pigment-printed inkjet ink composition according to the present embodiment contains a nonionic fluorosurfactant, the resulting printed product tends to be inferior in friction fastness. By using the particles, the pigment is easily fixed to the surface of the fabric, and even when a nonionic fluorosurfactant is used, a printed matter excellent in color development and friction fastness can be obtained.

  As the urethane resin, for example, it is preferable to contain a urethane resin containing a crosslinkable group, such as a polycarbonate-based urethane resin. Examples of the crosslinkable group include an isocyanate group and a silanol group, and it is preferable to use one in which the isocyanate group is chemically capped or blocked (blocked isocyanate group). The blocked isocyanate group is deprotected and activated by application of heat to form a bond (eg, urethane bond, urea bond, allophanate bond, etc.).

  Moreover, it is preferable that three or more crosslinkable groups of the urethane-based resin having a crosslinkable group are provided in one molecule. In such a case, a crosslinked structure is formed by the reaction of the crosslinkable group. In this specification, the urethane resin is a urethane bond or urea bond formed by reacting an isocyanate group with another reactive group (for example, a hydroxyl group, an amino group, a urethane bond group, a carboxyl group, etc.). It refers to a resin containing an allophanate bond or the like. Therefore, in this specification, for example, urea resin is included in urethane resin. The urethane resin is preferably a compound having a urethane bond obtained by reacting a compound having an isocyanate group with a compound having a hydroxyl group.

  Blocked isocyanate (chemically protected isocyanate) contains a latent isocyanate group in which an isocyanate group is blocked by a blocking agent, and can be obtained, for example, by reacting a polyisocyanate compound with a blocking agent.

  Examples of the polyisocyanate compound include polyisocyanate monomers and polyisocyanate derivatives. Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. , Etc.), allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-described polyisocyanate monomer with a low molecular weight polyol described later), polyol modified products (for example, polyisocyanate monomer and later-described). Modified polyols (alcohol adducts, etc.) produced by reaction with low-molecular-weight polyols, biuret-modified products (for example, biuret-modified products produced by reaction of the above polyisocyanate monomer with water or amines, etc.) ), Modified urea (for example, in the reaction of the above polyisocyanate monomer and diamine) Modified urea-modified products), oxadiazine trione-modified products (for example, oxadiazine trione produced by the reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (the above-mentioned polyisocyanate monomer). Carbodiimide-modified products produced by decarboxylation condensation reaction of monomers), uretdione-modified products, uretonimine-modified products, and the like.

  When two or more polyisocyanate compounds are used in combination, for example, at the time of production of blocked isocyanate, two or more polyisocyanate compounds may be reacted simultaneously, and each polyisocyanate compound is used individually. You may mix the blocked isocyanate obtained by this.

The blocking agent blocks the isocyanate group to inactivate it, but regenerates or activates the isocyanate group after deblocking, and activates the isocyanate group in the blocked and deblocked state of the isocyanate group. It also has a catalytic action.

  Blocking agents include imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, carbamic acid compounds. , Urea compounds, acid amide (lactam) compounds, acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, bisulfites and the like.

  Examples of the imidazole compound include imidazole (dissociation temperature 100 ° C.), benzimidazole (dissociation temperature 120 ° C.), 2-methylimidazole (dissociation temperature 70 ° C.), 4-methylimidazole (dissociation temperature 100 ° C.), 2-ethyl. Examples include imidazole (dissociation temperature 70 ° C.), 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and the like.

  Examples of the imidazoline-based compound include 2-methylimidazoline (dissociation temperature 110 ° C.), 2-phenylimidazoline, and the like.

  Examples of the pyrimidine compounds include 2-methyl-1,4,5,6-tetrahydropyrimidine.

  Examples of the guanidine-based compound include 3,3-dialkylguanidine such as 3,3-dimethylguanidine, for example, 1,1,3, such as 1,1,3,3-tetramethylguanidine (dissociation temperature 120 ° C.). 3-tetraalkyl guanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene and the like can be mentioned.

  Examples of the alcohol compound include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2 , 2-trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxy Ethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibutyl-2-hydroxyacetamide, N-hydro Cysuccinimide, N-morpholine ethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine (dissociation temperature 140 ° C.), furfuryl alcohol, 12-hydroxystearic acid , Triphenylsilanol, 2-hydroxyethyl methacrylate and the like.

Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n -Nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n -Nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicyla , Methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4-[(dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, bis (4-hydroxy Phenyl) acetic acid, 2-hydroxypyridine (dissociation temperature 80 ° C.), 2- or 8-hydroxyquinoline, 2-chloro-3-pyridinol, pyridine-2-thiol (dissociation temperature 70 ° C.), and the like.

  Examples of the active methylene compound include Meldrum's acid, dialkyl malonate (for example, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, malonic acid. Methyl n-butyl, ethyl n-butyl malonate, methyl s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, malon Diphenyl acid, benzyl methyl malonate, ethyl phenyl malonate, t-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (eg methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate) , N-butyl acetoacetate, t-acetoacetate Butyl acetoacetate benzyl, phenyl acetoacetate), 2-acetoacetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate and the like.

  Examples of the amine compound include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, diisopropylamine ( Dissociation temperature 130 ° C), isopropylethylamine, 2,2,4- or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine (dissociation temperature 140 ° C), dicyclohexylamine (dissociation temperature 130 ° C), Bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2,6-dimethylpiperidine (dissociation temperature 130 ° C), t-butylmethylamine, t-butylethylamine (dissociation temperature 120 ° C), t-butylpropylamine , T-butylbutylamine, t-butyl Nylamine (dissociation temperature 120 ° C.), t-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine (dissociation temperature 80 ° C.), (dimethylamino) -2,2, Examples include 6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

  Examples of the imine compound include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

  Examples of oxime compounds include formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime (dissociation temperature 130 ° C.), cyclohexanone oxime, diacetylmonooxime, benzophenoxime, 2,2,6,6-tetramethyl. Cyclohexanone oxime, diisopropyl ketone oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone Oxime, n-amyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzofe N'okishimu, 2-cycloheptanone oxime, and the like.

  Examples of the carbamic acid compound include phenyl N-phenylcarbamate.

  Examples of the urea compound include urea, thiourea, and ethylene urea.

Examples of the acid amide (lactam) compound include acetanilide, N-methylacetamide, acetic acid amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, laurolactam, and the like. It is done.

  Examples of the acid imide compound include succinimide, maleic imide, phthalimide, and the like.

  Examples of triazole compounds include 1,2,4-triazole, benzotriazole, and the like.

  Examples of the pyrazole compound include pyrazole, 3,5-dimethylpyrazole (dissociation temperature 120 ° C.), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-t-butylpyrazole, 3- Examples include methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole.

  Examples of mercaptan compounds include butyl mercaptan, dodecyl mercaptan, hexyl mercaptan, and the like.

  Examples of the bisulfite include sodium bisulfite.

  Furthermore, as a blocking agent, it is not limited to the above, For example, other blocking agents, such as a benzoxazolone, an isatoic anhydride, tetrabutylphosphonium acetate, are mentioned.

  In addition, about some compounds illustrated above, dissociation temperature was written together as temperature which reproduces | regenerates an isocyanate group.

  Such blocking agents can be used alone or in combination of two or more. The dissociation temperature of the blocking agent can be appropriately selected. The dissociation temperature is, for example, 60 ° C. or higher and 230 ° C. or lower, preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and further preferably 110 ° C. or higher and 160 ° C. or lower. Within such a temperature range, the pot life of the pigment-printed inkjet ink composition can be made sufficiently long, and the temperature in the heating step can be prevented from becoming too high.

  The main chain of the urethane resin having a crosslinkable group may be any of a polyether type including an ether bond, a polyester type including an ester bond, a polycarbonate type including a carbonate bond, and the like. When the urethane-based resin having a crosslinkable group is crosslinked (crosslinked product), the elongation at break and 100% modulus can be adjusted by changing the density of the crosslinking points and the kind of the main chain. . Among these, the urethane-based resin having a crosslinkable group having a polycarbonate skeleton or a polyether skeleton has a good balance between elongation at break and 100% modulus, friction fastness of an image, A polycarbonate-based urethane resin having a polycarbonate-based skeleton is more preferable because it tends to improve the texture. In particular, since the pigment-printed inkjet ink composition used in the present embodiment contains a nonionic fluorosurfactant, the resulting printed product tends to be inferior in friction fastness. By using resin particles, the pigment is easily fixed to the surface of the fabric, and even when a nonionic fluorosurfactant is used, a printed matter excellent in color development and friction fastness can be obtained.

The urethane-based resin having a crosslinkable group has an elongation at break of 150% or more, preferably 170% or more, more preferably 200% or more, further preferably 300, after the crosslinking is formed (crosslinked product). % Or more is preferable. By selecting the density of the cross-linking points and the type of the main chain so as to achieve such an elongation at break, the texture of the printed material can be improved.

  Here, the elongation at break is, for example, by curing a urethane resin emulsion having a crosslinkable group to prepare a film having a thickness of about 60 μm, under the conditions of a tensile test gauge length of 20 mm and a pulling speed of 100 mm / min. The value obtained by measuring with can be adopted. For the 100% modulus, a value obtained by measuring the tensile stress when the film is stretched 100% with respect to the original length in the tensile test can be adopted. The film to be measured may be formed using a urethane resin emulsion having a crosslinkable group, or may be formed by molding using the same kind of resin, but is preferably formed using an emulsion resin.

  The urethane resin having a crosslinkable group may be blended in the form of an emulsion. Such a resin emulsion is a so-called self-reactive urethane resin emulsion, and a commercially available urethane resin emulsion having an isocyanate group blocked with a blocking agent having a hydrophilic group can be used.

  Commercially available urethane resins having a crosslinkable group include Takelac WS-6021 (trade name, manufactured by Mitsui Chemicals Polyurethanes, urethane resin emulsion, polyether-based polyurethane having a polyether-derived skeleton), WS-5100 ( Product name, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., urethane-based resin emulsion, polycarbonate-based polyurethane having a polycarbonate-derived skeleton), Elastron E-37, H-3 (the polyester-based polyurethane whose main chain has a polyester-derived skeleton), Elastron H-38, BAP, C-52, F-29, W-11P (the above is a polyether polyurethane having a main chain having a polyether-derived skeleton) (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion) ), Superflex 870, 80 150, 420, 460, 470, 610, 700 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), Permarin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion) Sancure 2710 (trade name, manufactured by Nihon Lubrizol Corporation, urethane resin emulsion), NeoRez R-9660, R-9937, R-940 (trade name, manufactured by Enomoto Kasei Co., Ltd., urethane resin emulsion), Adeka Examples include Bontiter HUX-380, 290K (trade name, manufactured by ADEKA Corporation, urethane resin emulsion), and the like.

  In this embodiment, the content of the resin particles is preferably 1% by mass or more and 20% by mass or less with respect to the total mass (100% by mass) of the ink in terms of solid content, and the lower limit is 2.5% by mass. % Or more is more preferable, and it is further more preferable that it is 3 mass% or more. Further, the upper limit of the content of the resin particles is more preferably 15% by mass or less, and further preferably 12% by mass or less. By setting the content of the resin particles in the above range, it is possible to achieve both ejection stability and friction fastness of the obtained recorded matter.

  Note that these urethane resins may be included in the treatment liquid when the treatment liquid is used in the inkjet pigment printing method according to the present embodiment, which will be described later, and in that case, the urethane contained in the treatment liquid. The urethane resin contained in the pigment printing inkjet ink composition may be the same or different.

  In addition, the temperature of the heating step in the inkjet pigment printing method according to the present embodiment, which will be described later, is determined by considering the deprotection temperature (dissociation temperature) of the isocyanate group of the urethane resin having these crosslinkable groups. It is set so that at least a part is activated.

2.3. Surfactant The pigment textile printing inkjet ink composition used in the present embodiment may contain a surfactant. The surfactant has functions such as lowering the surface tension of the ink composition and improving wettability with the fabric, and the desired ink viscosity and surface required for the inkjet pigment printing method according to the present embodiment. It becomes easy to adjust to the tension.

  Among the surfactants, for example, acetylene glycol surfactants, acetylene alcohol surfactants, silicone surfactants, and fluorine surfactants can be preferably used. Among these, it is preferable to use a silicone-based surfactant and a fluorine-based surfactant from the viewpoint that the surface tension of the ink composition can be easily obtained.

  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 (all are trade names, manufactured by Air Products and Chemicals. Inc.), Olphin 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 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.).

  Although it does not specifically limit as a silicone type surfactant, A polysiloxane type compound is mentioned preferably. Although it does not specifically limit as the said polysiloxane type compound, For example, polyether modified organosiloxane is mentioned. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, Big Chemie Japan 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 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

  As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer. As a specific example, BYK-340 (manufactured by Big Chemie Japan Co., Ltd.) can be mentioned.

  The lower limit of the surfactant content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably with respect to the total mass (100% by mass) of the ink. It is 0.5 mass% or more. Further, the upper limit of the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass with respect to the total mass (100% by mass) of the ink. % Or less, particularly preferably 2% by mass or less, and more preferably 1% by mass or less.

  In the present embodiment, the fluorosurfactant is preferably a nonionic fluorosurfactant. When a nonionic fluorosurfactant is used, the ink is prevented from penetrating into the fabric by suppressing the penetration of the ink into the fabric by the action of holding the ink on the fabric surface. Further, since the surfactant is nonionic, uneven color development is less likely to occur. Therefore, when the pigment printing inkjet ink composition used in the present embodiment contains a nonionic fluorosurfactant, it is possible to obtain a printed product excellent in color developability.

  In addition, when the pigment-printed inkjet ink composition used in the present embodiment is used for two-layer printing, the surface of the white base formed by the white ink containing the white pigment as the pigment of the pigment-printed inkjet ink composition is wetted. By reducing the color property, bleeding at a color boundary with a chromatic color ink (hereinafter also referred to as “color ink”) to be printed later is reduced, so that the color development property of the chromatic color ink is improved.

  When selecting a nonionic fluorosurfactant, it is preferable to consider the HLB value. That is, the lower limit of the HLB value of the nonionic fluorosurfactant blended in the pigment printing inkjet ink composition is 6 or more, preferably 8 or more, more preferably 10 or more. Further, the upper limit of the HLB value of the nonionic fluorosurfactant is 15 or less, preferably 13 or less, more preferably 12 or less. A nonionic fluorosurfactant having an HLB value in the above range has higher hydrophilicity and can more easily suppress the penetration of a pigment-printed inkjet ink composition into a fabric. Therefore, the color developability can be further improved.

  In addition, the HLB value in this specification is the following formula (1) from the ratio of the nonpolar value (I) and the polar value (O) in the organic conceptual diagram (hereinafter also simply referred to as “I / O value”). Is a value calculated by

HLB value = (Nonpolar value (I) / Polarized value (O)) × 10 (1)
Specifically, I / O values are written by Atsushi Fujita, “Systematic Organic Qualitative Analysis Mixture”, Kazama Shobo, 1974; Norihiko Kuroki, “Dyeing Theoretical Chemistry”, Sakai Shoten, 1966; Hiroo Inoue , “Organic Compound Separation Method”, Suikabo, 1990.

  The nonionic fluorosurfactant preferably has a polyoxyethylene group and a fluorinated alkyl group, and is preferably a polyfluoroalkylamine oxide or a polyfluoroalkyl / alkylene oxide adduct.

  As the nonionic fluorosurfactant used in the present embodiment, commercially available ones can be used, and Surflon S-145, Surflon S-241, Surflon S-242, Surflon S-243, Surflon S-386, Surflon S-393, Surflon S-420, Surflon S-611, Surflon S-650, Surflon S-651, Surflon KH-20, Surflon KH-40 (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.) ), Fluorard FC-170C, Fluorard FC-430, Fluorard-FC4430 (all trade names, manufactured by Sumitomo 3M Japan Ltd.), FSO, FSO-100, FSN, FSN-100, FS-300 (all trade names, DuPont) ), FT-250, 25 (All trade names, Ltd. Neos), Megafac F-554, Megafac F-556 (all trade names, DIC Co., Ltd.), and the like. Among them, it is preferable to use DuPont's FSO, FSO-100, FSN, FSN-100, and FS-300. By using these nonionic fluorosurfactants, the penetrability of the pigment-printed inkjet ink composition into the fabric can be controlled, and the color development of the printed product can be further improved. In addition, when the pigment-printed inkjet ink composition used in the present embodiment is used for two-layer printing, it may be printed later by reducing the wettability of the surface of the white base formed with the white ink. Bleeding at the color boundary with the chromatic ink is reduced, and the color developability of the chromatic ink is improved.

The lower limit of the content of the nonionic fluorosurfactant in the pigment-printed inkjet ink composition used in the present embodiment is 0.1% by mass with respect to the total mass (100% by mass) of the pigment-printed inkjet ink composition. It is preferable that it is above, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. The upper limit of the content of the nonionic fluorosurfactant is the total mass (100 of the pigment printing inkjet ink composition).
% By mass) is preferably 0.8% by mass or less, more preferably 0.6% by mass or less, and further preferably 0.5% by mass or less. When the content of the nonionic fluorosurfactant is within the above range, the penetrability of the pigment-printed inkjet ink composition into the fabric can be controlled, and the color development of the printed product can be further improved. In addition, when the pigment-printed inkjet ink composition used in the present embodiment is used for two-layer printing, it may be printed later by reducing the wettability of the surface of the white base formed with the white ink. Bleeding at the color boundary with the chromatic ink is reduced, and the color developability of the chromatic ink is improved.

  In addition, when the pigment printing inkjet ink composition used in this embodiment is used for two-layer printing, the content of the nonionic fluorosurfactant in the chromatic pigment printing inkjet ink composition is the chromatic pigment printing inkjet. It is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and further preferably 0.1% by mass or less, based on the total mass (100% by mass) of the ink composition. . Due to the low content of nonionic fluorosurfactant in the chromatic pigment printing inkjet ink composition, the decrease in the friction fastness of the printed product obtained in two-layer printing is suppressed, and the abrasion resistance is good. An image is obtained.

2.4. Water The pigment printing inkjet ink composition used in the present embodiment contains water as a solvent. Water is a main medium of ink and is a component that evaporates and scatters when dried. Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. Further, 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 time.

  The content of water contained in the pigment-printed inkjet ink composition used in the present embodiment is not particularly limited, but is, for example, 50% by mass or more with respect to the total mass (100% by mass) of the ink. Furthermore, it can be 60 mass% or more, and can be 70 mass% or more. Further, the upper limit of the content of water contained in the ink can be 95% by mass or less, 90% by mass or less, and 80% by mass or less.

2.5. Water-soluble organic solvent The pigment-printed inkjet ink composition used in the present embodiment may contain a water-soluble organic solvent. By including the water-soluble organic solvent, it is possible to effectively suppress water evaporation from the ink-jet head when the ink composition is left standing for a long time while improving the ejection stability of the ink composition by the ink-jet method.

  Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, betaine compounds, and the like.

Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 to 6 carbon atoms in the molecule and having one ether bond in the molecule. Specific examples include 1,2-pentanediol, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether Glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 2-methyl-3-phenoxy-1,2-propanediol, 3- (3-methylphenoxy) -1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl- 2-phenoxymethyl- , 3-propanediol, 3-methyl-1,3-butanediol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,4-butanediol, 1,5-pentane Examples include glycols such as diol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol.

  Examples of glycol ethers include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. preferable. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

  A betaine compound is a compound that has a positive charge and a negative charge at non-adjacent positions in the same molecule, and has no positively charged hydrogen atoms bonded to dissociable hydrogen atoms, so that the molecule as a whole has no charge. (Inner salt). Preferred betaine compounds are N-alkyl substituted amino acids, more preferably N-trialkyl substituted amino acids. Examples of the betaine compound include trimethylglycine (also referred to as “glycine betaine”), γ-butyrobetaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and glutamic acid betaine. Preferably, a trimethylglycine etc. can be illustrated.

  A pyrrolidone derivative may be used as the water-soluble organic solvent. Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc.

  A plurality of water-soluble organic solvents may be used in combination. The water-soluble organic solvent is preferably added so as to have the desired viscosity and surface tension of the ink described later, and the content thereof is 0.2 mass relative to the total mass (100 mass%) of the ink. % To 30% by mass, preferably 0.4% to 20% by mass, more preferably 0.5% to 15% by mass, and still more preferably 0.7% to 10% by mass.

2.6. Inorganic Alkali Compound The pigment printing inkjet ink composition used in the present embodiment preferably contains an inorganic alkali compound (inorganic base compound). The inorganic alkali compound has a property of increasing the pH of the pigment printing inkjet ink composition. The inorganic alkali compound has at least a function of improving the dispersion stability of the resin particles and / or a function of improving the redispersibility of the resin particles.

  Inorganic alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates Examples include salts.

  Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of the alkaline earth metal hydroxide include calcium hydroxide and magnesium hydroxide.

  Examples of the alkali metal carbonate include lithium carbonate, lithium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like. Examples of the alkaline earth metal carbonate include calcium carbonate.

  Examples of the alkali metal phosphate include lithium phosphate, potassium phosphate, potassium dihydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, and the like. Examples of alkaline earth metal phosphates include calcium phosphate and calcium hydrogen phosphate.

  In the pigment printing ink-jet ink composition used in this embodiment, a plurality of the inorganic alkali compounds exemplified above may be used. The total content of the inorganic alkali compound is 0.01% by mass or more and 0.8% by mass or less, preferably 0.02% by mass or more and 0% by mass with respect to the total mass (100% by mass) of the pigment printing inkjet ink composition. .6 mass% or less, more preferably 0.03 mass% or more and 0.4 mass% or less, further preferably 0.04 mass% or more and 0.3 mass% or less, particularly preferably 0.05 mass% or more and 0.2 mass% or less. It is 0.05 mass% or less, More preferably, it is 0.05 mass% or more and 0.1 mass% or less.

  If the blending amount of the inorganic alkali compound is within such a range, the pH of the pigment printing inkjet ink composition can be sufficiently increased, and the function of increasing the dispersion stability of the resin particles and / or the redispersibility of the resin particles can be achieved. The function to improve can be exhibited.

2.7. Other components The pigment printing ink-jet ink composition used in the present embodiment comprises a pH adjuster, an antiseptic / an antifungal agent, a rust inhibitor, a chelating agent, a viscosity adjuster, a dissolution aid, and an antioxidant as necessary. An agent or the like may be contained.

<PH adjuster>
As the pH adjuster, in addition to the above inorganic alkali compounds, for example, amines having a standard boiling point at 25 ° C. of 200 ° C. or higher, such as morpholines, piperazines, diethanolamine, triethanolamine, triisopropanolamine, ammonia, etc. Can be mentioned. Among these, it is preferable to contain amines having a normal boiling point at 5 ° C. of 200 ° C. or more. By containing such a high-boiling amine, clogging of the head can be suppressed at the temperature of the heating step in the inkjet pigment printing method according to the present embodiment described later.

<Preservatives and fungicides>
Examples of preservatives and fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzthiazoline-3-one (ICI) Proxel CRL, Proxel BND, Proxel GXL, Proxel XL-2, Proxel TN) and the like.

<Chelating agent>
Chelating agents have the property of trapping ions. Examples of such a chelating agent include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate.

2.8. Method for preparing pigment-printed inkjet ink composition The pigment-printed inkjet ink composition used in the present embodiment is obtained by mixing the components described above in an arbitrary order and removing impurities by filtration or the like as necessary. It is done. As a method for mixing the components, 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 suitably used. As a filtration method, centrifugal filtration, filter filtration, or the like can be performed as necessary.

2.9. Physical Properties of Pigment-Printed Inkjet Ink Composition The pigment-printed inkjet ink composition used in this embodiment is applied to a fabric by an inkjet method. Therefore, the pigment textile inkjet ink composition preferably has a surface tension at 25 ° C. of 10 mN / m or more and 40 mN / m or less from the viewpoint of a balance between recording quality and reliability as an ink for inkjet recording, More preferably, it is at least 40 mN / m. The surface tension is measured by, for example, using an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) to confirm the surface tension when the platinum plate is wetted with ink in an environment of 25 ° C. Can be measured.

  From the same viewpoint, the viscosity of the pigment printed inkjet ink composition at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, more preferably 2 mPa · s or more and 5 mPa · s or less, more preferably 2 mPa · s. -More preferably, it is s or more and 3.6 mPa * s or less. The viscosity can be measured, for example, using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) in an environment of 40 ° C. or 20 ° C.

3. Inkjet Pigment Printing Treatment Liquid Composition Next, the inkjet pigment printing treatment liquid composition according to the present embodiment will be described. A treatment liquid composition for inkjet pigment printing according to the present embodiment is a treatment liquid composition that aggregates the components of the ink composition described above in inkjet pigment printing, and is used by adhering to a fabric, and is cationic. It contains a compound, a nonionic fluorosurfactant, resin particles, and water.

  Note that the treatment liquid composition for inkjet pigment printing according to this embodiment constitutes the treatment liquid composition set for inkjet pigment printing according to this embodiment, and the treatment liquid composition for inkjet pigment printing according to this embodiment. The set includes a treatment liquid composition for inkjet pigment printing according to the present embodiment and the above-described pigment printing inkjet ink composition.

3.1. Cationic Compound The treatment liquid composition for inkjet pigment printing according to the present embodiment contains a cationic compound. The cationic compound acts as an aggregating agent that aggregates the components of the ink composition, and examples thereof include polyvalent metal salts, organic acids, cationic resins, and cationic surfactants. These cationic compounds may be used alone or in combination of two or more. Among these cationic compounds, it is preferable to use a polyvalent metal salt, an organic acid or a cationic resin from the viewpoint of excellent reactivity with pigments and resin particles contained in the ink composition. More preferably, it is used.

The polyvalent metal salt is a compound that is composed of divalent or higher polyvalent metal ions and anions that bind to these polyvalent metal ions and is soluble in water. Specific examples of the polyvalent metal ions include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ and Ba ²⁺ ; trivalent metal ions such as Al ³⁺ , Fe ³⁺ and Cr ^3+. It is done. Examples of the anion include Cl ⁻ , I ⁻ , Br ⁻ , SO ₄ ²⁻ , ClO ³⁻ , NO ³⁻ , HCOO ⁻ , and CH ₃ COO ⁻ . Among these polyvalent metal salts, calcium salts and magnesium salts are preferable from the viewpoint of the stability of the treatment liquid and the reactivity as a flocculant, and any of calcium nitrate and calcium chloride is preferable.

  Examples of organic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. , Lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof Etc. are preferable. An organic acid may be used individually by 1 type, and may use 2 or more types together.

  Examples of the cationic resin include a cationic urethane resin, a cationic olefin resin, and a cationic allylamine resin.

  As a cationic urethane resin, a well-known thing can be selected suitably and can be used. As the cationic urethane resin, commercially available products can be used. For example, Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name, Dainippon Ink Chemical Co., Ltd.), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR-2122C (trade name, Taisei) Fine Chemical Co., Ltd.) can be used.

  The cationic olefin resin has an olefin such as ethylene or propylene in the structural skeleton, and a known one can be appropriately selected and used. Further, the cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, and examples thereof include Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Ltd.) and the like.

  As the cationic allylamine resin, known ones can be appropriately selected and used. For example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetate Copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate , Polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate It can be mentioned sulfur dioxide copolymers, methyl diallyl amine hydrochloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-acrylamide copolymer and the like. As such a cationic allylamine resin, commercially available products can be used. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL- 10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11- HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H- 5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (trade name, Nittobo Medical strain) Company, Ltd.), Haimo Neo-600, Haimorokku Q-101, Q-311, Q-501, high-Max SC-505, SC-505 (trade name, can be used Haimo Co., Ltd.), and the like.

Further, as the cationic resin, a compound obtained by polymerizing a monomer containing an amine and epihalohydrin can also be used. Such a compound contains a hydroxyl group, an ammonium cation or the like in the main chain, and also has a function of enhancing the buffering action and the action of aggregating the pigment when contacted with the ink by liberating the halogen anion in the aqueous solution. Conceivable. Examples of the compound obtained by polymerizing a monomer containing an amine and an epihalohydrin include a compound selected from a polyamine-epihalohydrin copolymer, a polyamide-epihalohydrin copolymer, a polyamide polyamine-epihalohydrin copolymer, and an amine-epihalohydrin copolymer. A suitable example is given. These compounds are obtained by a known method such as a method of polymerizing a monomer containing an amine and an epihalohydrin, or a method of graft polymerization of a monomer containing an epihalohydrin on a polyamide obtained by polymerizing a monomer containing an amine and a carboxylic acid. can get. The mass average molecular weight varies depending on the type of copolymer, and in the case of a polyamine-epihalohydrin copolymer, a range of 500 to 100,000 is preferable, and in the case of a polyamide-epihalohydrin copolymer or a polyamide polyamine-epihalohydrin copolymer, 10,000. The range of ˜5 million is preferable, and in the case of the amine-epihalohydrin copolymer, the range of 700 to 50,000 is preferable. If the mass average molecular weight exceeds each of the above upper limits, the aqueous solution may not be formed, and if the lower limit is not reached, the pretreatment effect may be reduced. Examples of commercially available products of such compounds include WS-4020 (manufactured by Seiko PMC Co., Ltd., polyamide-epichlorohydrin copolymer).

  Examples of the cationic surfactant include primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, Quaternary alkyl ammonium salts, alkyl pyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts and the like can be mentioned. Specific examples of the cationic surfactant include hydrochlorides such as laurylamine, coconutamine and rosinamine, acetates, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammonium Ethyl sulfate, dimethyl ethyl octyl ammonium ethyl sulfate, trimethyl lauryl ammonium hydrochloride, cetyl pyridinium chloride, cetyl pyridinium bromide, dihydroxyethyl lauryl amine, decyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl ammonium chloride, hexa Decyldimethylammonium chloride, octadec Dimethyl ammonium chloride.

  The content of the cationic compound may be, for example, from 0.1% by mass to 25% by mass and from 0.2% by mass to 20% by mass with respect to the total mass (100% by mass) of the treatment liquid. It may be 0.3 mass% or more and 10 mass or less. Further, the concentration of the flocculant may be 0.03 mol / kg or more in 1 kg of the treatment liquid. Moreover, in 1 kg of process liquid, 0.1 mol / kg or more and 1.5 mol / kg or less may be sufficient, and 0.2 mol / kg or more and 0.9 mol / kg or less may be sufficient.

3.2. Water The treatment liquid composition for inkjet pigment printing according to the present embodiment preferably uses water as a main solvent. This water is a component that evaporates and scatters by drying after the treatment liquid is adhered to the recording medium. As the water, the same water as exemplified in the ink described above can be used, and the illustration is omitted. The content of water contained in the treatment liquid can be, for example, 50% by mass or more, preferably 60% by mass or more, and more preferably 70% with respect to the total mass (100% by mass) of the treatment liquid. It is at least mass%, more preferably at least 80 mass%.

3.3. Nonionic Fluorosurfactant The processing liquid composition for inkjet pigment printing according to the present embodiment contains a nonionic fluorosurfactant surfactant. In the pigment printing method using the treatment liquid composition for inkjet pigment printing according to the present embodiment, the penetration of the ink into the fabric is suppressed by the action of holding the ink by the nonionic fluorosurfactant on the fabric surface. Suppresses the sinking of pigment into the fabric. Further, since the surfactant is nonionic, uneven color development is less likely to occur. Therefore, when the treatment liquid composition for inkjet pigment printing according to the present embodiment contains a nonionic fluorosurfactant, it is possible to obtain a printed material with excellent color development.

  Further, when the inkjet pigment printing treatment liquid composition according to the present embodiment is used for two-layer printing, the surface of the white base formed by the white ink containing the white pigment as the pigment of the pigment printing inkjet ink composition is used. By reducing the wettability, bleeding at a color boundary with a chromatic color ink (hereinafter also referred to as “color ink”) to be printed later is reduced, so that the color developability of the chromatic color ink is improved.

  When selecting a nonionic fluorosurfactant, it is preferable to consider the HLB value. That is, the lower limit of the HLB value of the nonionic fluorosurfactant blended in the ink jet pigment printing treatment liquid composition is 6 or more, preferably 8 or more, more preferably 10 or more. Further, the upper limit of the HLB value of the nonionic fluorosurfactant is 15 or less, preferably 13 or less, more preferably 12 or less. A nonionic fluorosurfactant having an HLB value in the above range has higher hydrophilicity and can more easily suppress the penetration of a pigment-printed inkjet ink composition into a fabric. Therefore, the color developability can be further improved.

  The nonionic fluorosurfactant preferably has a polyoxyethylene group and a fluorinated alkyl group, and is preferably a polyfluoroalkylamine oxide or a polyfluoroalkyl / alkylene oxide adduct.

  Moreover, as a nonionic fluorine-type surfactant used by this embodiment, the thing similar to said pigment printing inkjet ink composition can be used.

  The lower limit of the content of the nonionic fluorosurfactant in the treatment liquid composition for inkjet pigment printing according to the present embodiment is 0.000 relative to the total mass (100 mass%) of the treatment liquid composition for inkjet pigment printing. It is preferably 1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more. Further, the upper limit of the content of the nonionic fluorosurfactant is preferably 0.8% by mass or less with respect to the total mass (100% by mass) of the treatment liquid composition for inkjet pigment printing. It is more preferably 6% by mass or less, and further preferably 0.5% by mass or less.

3.4. Water-soluble organic solvent A water-soluble organic solvent may be added to the ink-jet pigment printing treatment liquid composition according to this embodiment. By adding a water-soluble organic solvent, the wettability of the treatment liquid with respect to the recording medium can be improved. As the water-soluble organic solvent, the same organic solvents as exemplified in the above ink composition can be used. Although content of the water-soluble organic solvent is not specifically limited, For example, it is 1 mass% or more and 40 mass% or less with respect to the total mass (100 mass%) of a process liquid.

3.5. Resin Particles Resin particles (resin emulsion) are blended in the treatment liquid composition for inkjet pigment printing according to the present embodiment for the purpose of improving the fastness to friction and suppressing the fluffing of the fabric. Moreover, color development is also improved by containing resin particles. As such resin particles, commercially available products can be used. For example, if it is a urethane resin, Superflex 500, 6E-2000, E-2500, E-4000, R-5000 (trade name, Daiichi Kogyo) Pharmaceutical Co., Ltd.), Adekabon titer HUX-822, 830 (trade name, manufactured by ADEKA Corporation). Examples of the vinyl acetate resin include Vinibrand 1245L, 2680, 2682, and 2684 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.). Examples of the acrylic resin include Boncoat AN-402, R-3310, and R-3360 (trade names, manufactured by Dainippon Ink Co., Ltd.).

  The lower limit of the content of the resin particles in the treatment liquid is preferably 1% by mass or more, and preferably 3% by mass or more with respect to the total mass (100% by mass) of the treatment liquid composition for inkjet pigment printing. Is more preferable, and it is further more preferable that it is 5 mass% or more. Further, the upper limit of the content of the resin particles is preferably 12% by mass or less, more preferably 10% by mass or less, with respect to the total mass (100% by mass) of the treatment liquid composition for inkjet pigment printing. Preferably, it is 8 mass% or less. When the content of the resin particles in the treatment liquid is in the above range, the friction fastness can be further improved and the fluffing of the fabric can be suppressed.

  In addition, in the treatment liquid composition for inkjet pigment printing according to the present embodiment, the resin particles are preferably nonionic or cationic resin particles. When the resin particles are nonionic resin particles, a printed matter excellent in color development and friction fastness can be obtained particularly in printing on cotton. Further, when the resin particles are cationic resin particles, a printed matter excellent in color development and friction fastness can be obtained particularly in printing on a fabric composed of polyester or polyester blended yarn.

3.6. Other Components A pH adjuster, antiseptic / antifungal agent, rust preventive agent, chelating agent, and the like may be added to the treatment liquid composition for inkjet pigment printing according to the present embodiment, if necessary. As other components, the same components as those exemplified in the above ink composition can be used.

3.7. Method for Preparing Inkjet Pigment Printing Treatment Liquid Composition The inkjet pigment printing treatment liquid composition according to this embodiment can be produced by dispersing and mixing the above-described components by an appropriate method. After sufficiently stirring each of the above components, filtration can be performed to remove coarse particles and foreign matters that cause clogging, thereby obtaining a target treatment liquid.

3.8. Physical Properties of Inkjet Pigment Printing Treatment Liquid Composition The inkjet pigment printing treatment liquid composition according to this embodiment has a surface tension at 20 ° C. of 20 mN / m or more and 40 mN / m when ejected by an ink jet recording head. It is preferable that it is 20 mN / m or more and 35 mN / m or less. The surface tension is measured by, for example, measuring the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. using an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.). It can be measured by checking.

  From the same viewpoint, the viscosity at 20 ° C. of the treatment liquid composition for inkjet pigment printing according to this embodiment is preferably 3 mPa · s or more and 10 mPa · s or less, preferably 3 mPa · s or more and 8 mPa · s or less. More preferably. The viscosity can be measured, for example, by using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) under a 20 ° C. environment.

3.9. As described above, according to the treatment liquid composition for ink-jet pigment printing according to the present embodiment, the action of retaining the ink by the nonionic fluorosurfactant on the fabric surface causes the ink to enter the fabric. Suppressing the penetration of the pigment into the fabric. Further, since the surfactant is nonionic, uneven color development is less likely to occur. As described above, when the treatment liquid composition for inkjet pigment printing contains a nonionic fluorosurfactant, the penetration of the ink into the fabric is controlled, and a printed product excellent in color developability, particularly white color developability. can get. In addition, the inkjet pigment printing treatment liquid composition comprising the inkjet pigment printing treatment liquid composition according to the present embodiment and the above-described pigment printing inkjet ink composition provides a printed material having excellent color development properties. In two-layer printing in which pigment printing using an ink containing a chromatic pigment is performed on the pigment printing using the pigment printing inkjet ink composition, a printed matter having excellent color development is obtained.

4). Fabric The inkjet pigment printing method according to the present embodiment is performed using a fabric. The material constituting the fabric is not particularly limited. For example, natural fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable materials such as polylactic acid. Examples thereof include fibers, and these blended fibers may be used. As the fabric, the above-described fibers may be any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Further, the basis weight of the fabric used in the present embodiment is not particularly limited, and is 1.0 oz (ounce) or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8 or less. 0.0 oz or less, more preferably 4.0 oz or more and 7.0 oz or less. If the fabric weight is within such a range, good recording (printing) can be performed. Furthermore, the inkjet pigment printing method according to the present embodiment can be applied to a plurality of types of fabrics having different basis weights, and good recording can be performed.

  In the present embodiment, the fabric can be a fabric composed of polyester or polyester blended yarn. Examples of such a fabric include a polyester fabric and a polyester blend fabric. Examples of the polyester blend fabric include a fabric in which polyester is blended in an amount of 20% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. Can be given. Such a polyester-containing fabric is excellent in that moisture such as sweat is easily dried, but on the other hand, in ink jet printing, the ink is likely to sink downward, and the pigment and the resin are not easily fixed. In the present embodiment, since printing is performed using the above-described nonionic fluorosurfactant-containing treatment liquid composition for inkjet pigment printing, the fabric is made of polyester or polyester blended yarn that easily sinks downward. Also in pigment printing, it can be made excellent in color developability.

5). Inkjet Pigment Printing Method Next, the inkjet pigment printing method according to this embodiment will be described for each step. The ink-jet pigment printing method according to the present embodiment includes a step of attaching the pigment-printing ink-jet ink composition to the region where the ink-jet pigment printing processing liquid composition is attached by the ink-jet method.

5.1. Treatment Liquid Composition Adhesion Step In the inkjet pigment printing method according to the present embodiment, in order to improve the color development of the printed matter, the ink composition treatment for aggregating the components of the ink composition before the ink is attached to the fabric. A treatment liquid composition attaching step for attaching the liquid composition to the fabric;

As the treatment liquid composition for inkjet pigment printing to be adhered to the fabric, the above-described treatment liquid composition for inkjet pigment printing is used. The amount of the treatment liquid composition attached is preferably 0.02 g / cm ² or more and 0.5 g / cm ² or less, for example, and preferably 0.02 g / cm ² or more and 0.24 g / cm ² or less. It is more preferable to make it adhere. By setting the adhesion amount of the treatment liquid composition within the above range, it becomes easy to uniformly apply the treatment liquid composition to the fabric, and it is possible to suppress image aggregation unevenness and enhance color development.

Further, in the treatment liquid composition adhesion step, when the treatment liquid composition contains a polyvalent metal salt, the amount of polyvalent metal salt contained in the treatment liquid composition adhered to the fabric is 1.6 μmol / it is preferable to adhere to the cm ² or more 6Myumol / cm ² or less, and more preferably be attached such that the 2 [mu] mol / cm ² or more 5 [mu] mol / cm ² or less. By attaching the polyvalent metal salt so that the amount of the polyvalent metal salt is 1.6 μmol / cm ² or more, the color developability of the recorded image is improved. Further, by attaching the polyvalent metal salt so that the amount of the polyvalent metal salt is 6 μmol / cm ² or less, the friction fastness of the recorded image is improved.

  Examples of the method for attaching the treatment liquid composition to the fabric include a method of immersing the fabric in the treatment liquid composition (dip coating), a method of applying the treatment liquid composition with a roll coater or the like (roller coating), and a treatment liquid. Examples thereof include a method of spraying the composition with a spray device or the like (spray coating), a method of spraying the treatment liquid composition with an ink jet method (inkjet coating), and the like, and any method may be used. Here, when inkjet printing is performed using the printer 1 shown in FIG. 1, the treatment liquid composition is preferably attached to the fabric M from the inkjet head 2 by inkjet coating. When the treatment liquid composition attaching step is performed by inkjet coating, the treatment liquid composition can be more uniformly attached to the fabric M.

  The inkjet pigment printing method according to the present embodiment may include a treatment liquid composition drying step of drying the treatment liquid composition attached to the fabric after the treatment liquid composition adhesion step. Although the treatment liquid composition may be dried by natural drying, drying with heating is preferable from the viewpoint of improving the drying speed. When heating is performed in the drying step of the treatment liquid composition, the heating method is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Moreover, as a heat source for heating, for example, an infrared ray (lamp) is used.

5.2. Ink composition adhesion step In the ink composition adhesion step, the pigment-printed inkjet ink composition used in the present embodiment is adhered to the fabric in the region where the ink-jet pigment printing treatment liquid composition is adhered. In addition, the ink composition attaching step may include a step of attaching the chromatic color pigment printed inkjet ink composition on the region where the pigment printed inkjet ink composition is adhered. When the ink composition adhesion step includes these two steps, a two-layer print in which an image is formed by the chromatic pigment printed inkjet ink composition is recorded on the image formed by the pigment printed inkjet ink composition. The

  The inkjet pigment printing method according to the present embodiment has a treatment liquid composition adhesion step using the treatment liquid composition for inkjet pigment printing containing the nonionic fluorosurfactant. Permeation of the ink is suppressed. Further, the ink component aggregates due to the reaction or interaction between the cationic compound of the treatment liquid composition and the ink component. As a result, a printed material having excellent color developability can be obtained.

In the ink composition adhesion step, when the pigment-printed inkjet ink composition is a white pigment-printed inkjet ink composition, the maximum adhesion amount to the fabric is 50 mg / cm ² or more and 200 mg / cm ² or less. It is preferable to adhere to 80 mg / cm ² or more and 150 mg / cm ² or less, and it is more preferable to adhere to 90 mg / cm ² or more and 130 mg / cm ² or less. When the maximum adhesion amount of the white pigment printing inkjet ink composition is as described above, the white color developability is good, and the color development particularly when adhering to a dark fabric is excellent, which is preferable as a background image. Further, it is preferable that the adhesion amount is in the above range since the image has excellent friction fastness and the aggregation unevenness tends to be inconspicuous.

On the other hand, in the ink composition adhesion step, the maximum adhesion amount of the chromatic pigment printed inkjet ink composition can be 1 mg / cm ² or more and 200 mg / cm ² or less, preferably 1 mg / cm ² or more and 30 mg / cm ² or more. ² or less, more preferably 2 mg / cm ² or more and 25 mg / cm ² or less, more preferably 5 mg / cm ² or more and 20 mg / cm ² or less, and particularly preferably 7 mg / cm ² or more and 15 mg / cm ² or less. This is preferable in that the color developability of the printed image is good, the drying property of the recorded image is good, the bleeding of the image can be suppressed, and the image such as a picture or character can be recorded on the fabric with good reproducibility.

5.3. Heating Step The inkjet pigment printing method according to the present embodiment preferably includes a step of heating the fabric during the ink composition attaching step. In ink jet textile printing, if the fabric is heated during the ink composition attaching step, the ink temperature is high, the viscosity and surface tension are lowered, and the ink is easily spread and spreads uniformly on the fabric. In this embodiment, since the permeation of the ink is controlled by the nonionic fluorosurfactant contained in the ink composition, the ink spreads on the fabric surface appropriately and uniformly. Thereby, the ink is easily fixed on the fabric, and the obtained recorded matter has improved leveling properties and excellent friction fastness. Moreover, by allowing the ink composition to adhere to the heated fabric, the drying property of the ink can be improved, the drying time can be shortened, and damage to the fabric can be suppressed.

  As a heating method for heating the ink composition applied to the fabric, there is a heating mechanism 6 shown in FIG. In addition to the above-described mechanism, these heating mechanisms include a heat press method, a normal pressure steam method, a high pressure steam method, a hot air drying method, and a thermofix method.

  In the heating step, the surface temperature of the heated fabric is 35 ° C. or more and 65 ° C. or less. When the surface temperature of the fabric surface is within the above range, damage to the ink jet head and the fabric can be reduced, and the ink can easily spread and penetrate into the fabric uniformly. In addition, the heating temperature in this heating process means the surface temperature of the heated fabric, for example, can be measured using a non-contact thermometer (trade name “IT2-80”, manufactured by Keyence Corporation). it can. The surface temperature of the heated fabric surface is preferably 40 ° C. or higher, and more preferably 45 ° C. or higher. Moreover, it is preferable that the upper limit of surface temperature is 60 degrees C or less, and it is more preferable that it is 55 degrees C or less.

  Further, the heating time is not particularly limited as long as the surface of the fabric is in the above temperature range. For example, the heating time can be 5 seconds or more and 1 minute or less, preferably 10 seconds or more and 30 seconds or less. is there. When the heating time is in the above range, the fabric can be sufficiently heated while reducing damage to the inkjet head and the fabric.

  In addition to the main heating step, as described with reference to FIG. 1, the second heating mechanism is provided downstream in the conveyance direction of the fabric M, and the fabric M after the ink composition attaching step is heated or dried. You may have a process. In this case, it is installed downstream of the heating mechanism 6 in FIG. Thereby, it is possible to improve the drying property of the ink droplets attached to the fabric M. Any of the mechanisms described in the heating mechanism 6 (for example, a dryer mechanism) can be used as the second heating mechanism.

The heating temperature in this case is not limited to this, but is preferably 100 ° C. or higher and 200 ° C. or lower. When the fabric is cotton, it is preferably 120 ° C. or higher and 160 ° C. or lower, When the fabric is composed of polyester or polyester blended yarn, it is more preferably 100 ° C. or higher and 140 ° C. or lower. When the heating temperature is within the above range,
It is possible to promote the reduction of fabric damage and the formation of a film of resin particles contained in the ink composition. The heating time is not limited to this, but it can be, for example, 30 seconds or more and 20 minutes or less, preferably 2 minutes or more and 7 minutes or less, more preferably 3 minutes or more and 5 minutes or less. It is. When the heating time is within the above range, it is possible to sufficiently dry the ink while reducing the damage to the fabric.

5.4. As described above, according to the inkjet pigment printing method according to the present embodiment, the ink composition is deposited on the ink-jet pigment printing treatment liquid composition according to the present embodiment. Infiltration of the ink adhered in the process is suppressed. Further, the ink component aggregates due to the reaction or interaction between the cationic compound of the treatment liquid composition and the ink component. As a result, a printed material having excellent color developability can be obtained.

6). Examples and Comparative Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

6.1. Preparation of white ink Each component was put into a container so as to have the composition shown in Table 1, mixed and stirred for 2 hours with a magnetic stirrer, and further dispersed in a bead mill filled with zirconia beads having a diameter of 0.3 mm. Mix well by doing. After stirring for 1 hour, each textile printing ink-jet ink composition was obtained by filtering using a 5 μm PTFE membrane filter. The numerical values in Table 1 indicate mass%, and pure water (ion exchange water) was added so that the total mass of each white ink was 100 mass%.

In Table 1, the details of the components described other than the compound names are as follows.
Water-dispersible resin: Takelac WS-5100 (trade name, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., polycarbonate-based urethane resin containing a blocked isocyanate as a crosslinkable group, the numerical values in the table are the solid content of the urethane resin .)
・ Fluorine-based surfactant: FS-300 (trade name, manufactured by DuPont, nonionic type)

6.2. Preparation of treatment liquid composition Each component was put in a container so as to have the composition of Tables 2 and 3, and ion-exchanged water was added and mixed and stirred so that the total mass was 100% by mass to obtain a treatment liquid. .

In Tables 2 and 3, the details of the components other than the compound names are as follows.
Cationic compound: WS-4020 (trade name, manufactured by Seiko PMC Co., Ltd., polyamide-epichlorohydrin copolymer)
Cationic resin: Vinibrand 1008 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., cationically modified product with good focusing properties, mainly composed of modified vinyl acetate, solid content 50%)
・ Nonionic resin: VINYBRAN 1245L (trade name, manufactured by Nissin Chemical Industry Co., Ltd., vinyl acetate / acrylic acid ester, solid content 40%)
・ Fluorine-based surfactant: FS-300 (trade name, manufactured by DuPont, nonionic type)
Fluorine-based surfactant: S-241 (trade name “Surflon S-241”, manufactured by AGC Seimi Chemical Co., Ltd., nonionic type)
Fluorine-based surfactant: S-221 (trade name “Surflon S-221”, manufactured by AGC Seimi Chemical Co., Ltd., nonionic type)
Acetylene-based surfactant; E1010 (trade name “Orphine E1010”, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol-based surfactant)

6.3. Production of printed material 6.3.1. A commercially available T-shirt fabric was prepared as a pretreatment fabric, and the treatment liquid composition obtained above was uniformly applied to the fabric using a roller so as to be 18 to 20 g per A4. After the treatment liquid was applied, heat treatment was performed at 160 ° C. for 1 minute using a heat press. The following three types of T-shirt fabric were used.
<T-shirt fabric>
・ Cotton (made by Hanes, heavyweight black 100% cotton)
・ PES (grimmer ACTIVE WEAR 3.5oz dry T-shirt black 100% polyester)
・ Mixed fiber (Printstar 4.6 oz. Honeycomb mesh T-shirt Black Cotton / Polyester: 45/55)

6.3.2. White ink printing White ink was applied to the fabric after the pretreatment by an inkjet method using an inkjet printer (PX-G930: manufactured by Seiko Epson Corporation). The printing pattern had a resolution of 1440 × 1440 dpi, and printing was performed under the condition that the solid printing was repeated four times to obtain a fabric printed with white ink. Thereafter, in order to confirm the whiteness, the printed fabric was heat-treated at 160 ° C. for 1 minute with a heat press machine to fix the white ink on the fabric, thereby obtaining a fabric printed with the white ink.

6.4. Evaluation test The obtained fabric was evaluated for whiteness and abrasion resistance.

6.4.1. Evaluation of color developability For the fabric after printing, using a commercially available colorimeter (product name “Gretag Macbeth Spectrolino”, manufactured by X-Rite), CIE / L ^* a ^* b ^{* in the} color system, L ^* values were measured and judged according to the following evaluation criteria. When the evaluation result is B or more, it can be said that the effect of the present invention is obtained.
(Evaluation criteria)
A: 80 ≦ L ^*
B: 75 ≦ L ^* <80
C: 70 ≦ L ^* <75
D: 65 ≦ L ^* <70
E: L ^* <65

6.4.2. Evaluation of Friction Fastness A dyed fastness test against friction was performed on the fabric after printing in accordance with a drying test specified in ISO-105 X12 using a type I (clock meter) tester. Evaluation was made using a contaminated gray scale. The evaluation criteria are as follows, and the results are shown in the table.
(Evaluation criteria)
A: Friction fastness is grade 4 or higher.
B: Friction fastness is 3rd grade or more and less than 4th grade.
C: Friction fastness is 2 or more and less than 3
D: Friction fastness is less than second grade.

6.4.3. Evaluation of treatment liquid storage stability The obtained treatment liquid was put into a sample bottle and allowed to stand at 60 ° C. for 10 days. Then, the presence or absence of foreign matter generation | occurrence | production visually and confirmation of printed matter were performed, and it determined by the following evaluation criteria.
(Evaluation criteria)
A: There is no generation of foreign matter and the printed matter has no problem.
B: There is no problem with the printed matter although some foreign matter is observed.
C: The occurrence of foreign matter was confirmed, and there was a slight change in the quality of the printed matter.

6.5. Evaluation results In Comparative Examples 1 to 6, which are out of the scope of the present invention, the results were low in color developability. First, Comparative Example 1 containing no cationic compound resulted in low color developability. Further, Comparative Example 2 containing a cationic compound but not containing resin particles resulted in low color developability and friction fastness. In Comparative Example 3 containing no nonionic fluorosurfactant, the color development was the lowest. In Comparative Example 4 which was printed on cotton with the combination of Comparative Example 3, although slightly higher than Comparative Example 3, the color developing property was still low. In Comparative Examples 5 and 6 using a surfactant other than the nonionic fluorosurfactant, the color developability was still low.

  In contrast to Comparative Examples 1 to 6, Examples 1 to 19 all had high color developability. In Example 1, with respect to the PES used as the fabric, not only the coloring property but also the fastness to friction and the storage stability of the treatment liquid were high. The same results as in Example 1 were obtained in Examples 2 and 3 printed on other fabrics in the combination of Example 1.

  In Example 4 using a nonionic resin as the resin particles, the color developability was slightly lowered. In Example 5 using a nonionic fluorosurfactant different from Example 1 as the surfactant, as in Example 1, all evaluations were high.

  In Example 6 in which white ink different from Example 1 was used, the color developability was slightly lowered because the surfactant of the ink was acetylene. Unlike Example 1, in Example 7 where acetic acid was used as the cationic compound, the color developability was slightly lowered.

  In Example 8, in which the content of the cationic compound was low as compared with Example 1, the color developability was slightly lowered. On the other hand, in Example 9, in which the content of the cationic compound is high compared to Example 1, the storage stability of the processing solution is slightly lowered, and in Example 15, where the content is high, the storage stability of the processing solution is low. It was.

  In Example 10, in which the content of the resin particles is lower than that in Example 1, the color developability was slightly lowered. On the other hand, in Example 11 in which the content of the resin particles is higher than that in Example 1, the treatment liquid storage stability is slightly lowered, and in Example 16 in which the content is higher, the treatment liquid storage stability is low. .

  In Example 12, in which the content of the nonionic fluorosurfactant was lower than that in Example 1, the color developability was slightly lowered. On the other hand, in Example 13, in which the content of the nonionic fluorosurfactant is higher than that in Example 1, the storage stability of the treatment liquid is slightly lowered, and in Example 17, in which the content is higher, the friction fastness and the treatment are increased. The liquid storage stability was low.

  In Example 14 using a polyvalent metal salt different from Example 1, all the evaluations were high as in Example 1.

  In Example 18 in which a cationic compound different from Example 1 was used, the color fastness was slightly lowered as compared with Example 1, but the friction fastness was high. In Example 19 using the color ink, the same result as in Example 1 was obtained.

  The present invention is not limited to the above-described embodiments, and various modifications can be made. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

  DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Inkjet head, 3 ... Ink cartridge, 4 ... Carriage, 5 ... Platen, 6 ... Heating mechanism, 7 ... Carriage moving mechanism, 8 ... Medium feed mechanism, 9 ... Guide lot, 10 ... Linear encoder, M ... Fabric, CONT ... Control device

Claims (11)

In inkjet pigment printing, a treatment liquid composition used by adhering to a fabric,
A treatment liquid composition for ink-jet pigment printing, comprising a cationic compound, a nonionic fluorosurfactant, resin particles, and water.   The treatment liquid composition for inkjet pigment printing according to claim 1, wherein the fabric is composed of polyester or polyester blended yarn.   The treatment liquid composition for inkjet pigment printing according to claim 1 or 2, wherein the cationic compound is a polyvalent metal salt, an organic acid, or a cationic resin.   The treatment liquid composition for inkjet pigment printing according to any one of claims 1 to 3, wherein the cationic compound contains either calcium nitrate or calcium chloride.   5. The treatment liquid composition for ink-jet pigment printing according to claim 1, wherein the nonionic fluorosurfactant has an HLB value in the range of 6 to 15. 5.   The treatment liquid composition for inkjet pigment printing according to any one of claims 1 to 5, wherein the nonionic fluorine-based surfactant has a polyoxyethylene group and a fluorinated alkyl group.   The treatment liquid composition for inkjet pigment printing according to any one of claims 1 to 6, wherein the resin particles are nonionic or cationic resin particles. A treatment liquid composition for inkjet pigment printing according to any one of claims 1 to 7,
A set for inkjet pigment printing comprising a pigment printing inkjet ink composition containing a pigment, resin particles, and water.   The set for inkjet pigment printing according to claim 8, wherein the resin particles contained in the pigment printing inkjet ink composition contain a polycarbonate-based urethane resin.   The ink-jet pigment printing set according to claim 8 or 9, wherein the pigment-printing ink-jet ink composition further contains a fluorine-based surfactant.   An ink-jet pigment printing method comprising a step of adhering a pigment-printing ink-jet ink composition by an ink-jet method to a region to which the ink-jet pigment printing treatment liquid composition according to any one of claims 1 to 7 is attached. .

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