JP7077709B2 - Aqueous inkjet composition - Google Patents

Description

The present invention relates to an aqueous inkjet composition.

In recent years, the use of inkjet printing has expanded, and it has been applied not only to printing machines for offices and homes, but also to commercial printing and textile printing.
Inkjet inks containing disperse dyes are also used.

Such ink for inkjet includes a direct printing method in which an ink is applied (printed) to a recording medium to be dyed (usually composed of fibers) and then dyed by heat treatment such as steaming. There is a thermal transfer printing method in which dye ink is applied (printed) to an intermediate transfer medium (dedicated transfer paper) and then the dye is sublimated and transferred from the intermediate transfer medium side to a recording medium to be dyed by heat.

Inkjet inks containing disperse dyes generally have a problem that the storage stability of the ink is low and the ejection stability by the inkjet method is also inferior due to the problem of long-term dispersion stability of the disperse dye.

For the purpose of solving such a problem, the ink composition described in Patent Document 1 has been proposed.

International Publication WO2005 / 121263 Gazette

However, in such an ink composition, when a specific disperse dye is contained, the storage stability of the ink composition cannot be sufficiently excellent, and long-term storage causes remarkable generation of foreign substances and inkjet. There is a problem that the head filter and the nozzle are clogged at the time of ejection by the method. In particular, as the disperse dye, C.I. I. The present inventor has found that such a problem becomes remarkable when Disperse Red 60 is used. In particular, C.I. I. Ink compositions containing Disperse Red 60 are prone to generate foreign matter (particularly crystalline foreign matter) at the gas-liquid interface, which is particularly likely to cause clogging of the head filter and nozzles during ejection by the inkjet method. I was finding it.

The present invention has been made to solve the above-mentioned problems, and can be realized as the following application examples.

（式（１）中、Ｒ^１、Ｒ^２のうちの一方は、－（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^３（ただし、Ｒ^３は、Ｈ、ＣＨ_３またはＣ_２Ｈ_５であり、ｎは１以上の整数である。）または－ＣＨ_２ＣＨ（ＣＨ_３） _２ であり、他方は、－Ｈであり、ｘおよびｙは、ｘが１のとき、ｙが０．２以上１．０以下となる関係である。） [1] C.I. I. Disperse Red 60 and
An aqueous inkjet composition comprising a styrene-maleic acid-based dispersant represented by the following formula (1).

(In the formula (1), one of R ¹ and R ² is-(CH ₂ CH ₂ O) _n R ³ (where R ³ is H, CH ₃ or C ₂ H ₅ and n is. It is an integer of 1 or more.) Or -CH ₂ CH (CH ₃ ) ₂ , the other is -H, and x and y are 0.2 or more and 1.0 or less when x is 1. It is a relationship that becomes.)

[2] The above-mentioned C.I. I. When the content of Disperse Red 60 is XD [mass%] and the content of the styrene maleic acid-based dispersant is XM [mass%], the above relationship of 0.04 ≦ XM / XD ≦ 25 is satisfied [1]. ] The aqueous inkjet composition according to the above.

[3] The above-mentioned C.I. I. The composition for an aqueous inkjet according to the above [1] or [2], wherein the content of Disperse Red 60 is 0.1% by mass or more and 30% by mass or less.

[4] The aqueous inkjet composition according to any one of [1] to [3] above, wherein the content of the styrene maleic acid-based dispersant is 0.1% by mass or more and 30% by mass or less.

[5] The aqueous inkjet composition according to any one of [1] to [4] above, wherein the styrene-maleic acid-based dispersant has a weight average molecular weight of 7,000 or more and 20,000 or less.

[6] Further containing an acetylene-based surfactant, the content of the acetylene-based surfactant is the above-mentioned C.I. I. Disperse Red 60: The aqueous inkjet composition according to any one of [1] to [5] above, which is 5.0 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass.

[7] The aqueous inkjet composition according to any one of claims 1 to 6, wherein the surface tension at 25 ° C. is 20 mN / m or more and 50 mN / m or less.

[8] The aqueous inkjet composition according to any one of [1] to [7] above, wherein the viscosity at 25 ° C. is 2 mPa · s or more and 30 mPa · s or less.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Composition for water-based inkjet>
By the way, among various disperse dyes, C.I. I. While the Disperse Red 60 has features such as excellent color development, it has the following problems. That is, C.I. I. Conventionally, when Nozzle Red 60 is used as a constituent component of an aqueous inkjet composition, the storage stability of the aqueous inkjet composition cannot be sufficiently excellent, and foreign substances are noticeable due to long-term storage. There was a remarkable problem that the head filter and the nozzle were clogged when the head filter and the nozzle were ejected by the inkjet method.

Therefore, the inventor of the present invention is C.I. I. We have conducted diligent research with the aim of providing an aqueous inkjet composition that can effectively prevent the above-mentioned problems from occurring while making the best use of the features of Disperse Red 60.
As a result, the present invention has been reached.

That is, the composition for an aqueous inkjet of the present invention is C.I. I. It is characterized by containing Disperse Red 60 and a styrene-maleic acid-based dispersant represented by the following formula (1).

（式（１）中、Ｒ^１、Ｒ^２のうちの一方は、－（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^３（ただし、Ｒ^３は、Ｈ、ＣＨ_３またはＣ_２Ｈ_５であり、ｎは１以上の整数である。）、－ＣＨ_２ＣＨ（ＣＨ_３）_２または－（ＣＨ_２）_３ＣＨ_３であり、他方は、－Ｈ、－（ＣＨ_２ＣＨ_２Ｏ）_ｎＲ^３（ただし、Ｒ^３は、Ｈ、ＣＨ_３またはＣ_２Ｈ_５であり、ｎは１以上の整数である。）、－ＣＨ_２ＣＨ（ＣＨ_３）_２、－（ＣＨ_２）_３ＣＨ_３または塩を構成する対イオンであり、ｘおよびｙは、ｘが１のとき、ｙが０．２以上１．０以下となる関係である。）

(In the formula (1), one of R ¹ and R ² is-(CH ₂ CH ₂ O) _n R ³ (where R ³ is H, CH ₃ or C ₂ H ₅ and n is. It is an integer of 1 or more), -CH ₂ CH (CH ₃ ) ₂ or-(CH ₂ ) ₃ CH ₃ , and the other is -H,-(CH ₂ CH ₂ O) _n R ³ (however, R ³ is H, CH ₃ or C ₂ H ₅ , where n is an integer greater than or equal to 1), —CH ₂ CH (CH ₃ ) ₂ , − (CH ₂ ) ₃ CH ₃ or a salt. It is a counter ion, and x and y have a relationship in which y is 0.2 or more and 1.0 or less when x is 1.)

With such a structure, C.I. is a disperse dye having features such as excellent color development in a low temperature process due to a relatively small molecular weight. I. While obtaining the effect of containing Disperse Red 60, remarkable generation of foreign matter (particularly crystalline foreign matter at the gas-liquid interface) due to long-term storage and clogging of the head filter and nozzle during ejection by the inkjet method occur. A difficult aqueous inkjet composition can be provided.

On the other hand, when the above-mentioned styrene-maleic acid-based dispersant is not used, or instead of the above-mentioned styrene-maleic acid-based dispersant, another dispersant (for example, a dispersant other than the styrene-maleic acid-based dispersant or styrene-maleic acid) is used. Even if it is a system dispersant, when a dispersant other than the one represented by the above chemical formula is used), the above-mentioned excellent effect cannot be obtained.

For example, in the above formula (1), when x is 1 and y is less than 0.2, the maleic acid skeleton is smaller than the styrene skeleton, so that C.I. I. The dispersion stability of Disperse Red 60 cannot be ensured, and foreign substances are likely to be generated during long-term storage of the aqueous inkjet composition.

Further, in the above formula (1), when x is 1 and y is more than 1.0, the styrene skeleton is smaller than that of the maleic acid skeleton. I. Since the dispersant has poor adsorptivity to the Disperse Red 60 and the dispersant is likely to be detached, foreign matter is likely to be generated during long-term storage of the aqueous inkjet composition.

In the present specification, the aqueous inkjet composition is a concept including not only the ink itself ejected by the inkjet method but also the undiluted solution used for preparing the ink. In other words, the aqueous inkjet composition of the present invention may be discharged as it is by an inkjet method, or may be discharged by an inkjet method after a treatment such as dilution. good.

[Styrene maleic acid-based dispersant]
The aqueous inkjet composition of the present invention contains a styrene-maleic acid-based dispersant represented by the above formula (1).

The styrene-maleic acid-based dispersant is C.I. I. By using it in combination with Disperse Red 60, C.I. I. Dispersion stability in the aqueous inkjet composition of Disperse Red 60 and storage stability of the aqueous inkjet composition can be made excellent, and when foreign matter is remarkably generated due to long-term storage or when ejected by the inkjet method. It is possible to effectively prevent the occurrence of clogging of the head filter and nozzle. As a result, the water-based inkjet composition can be stably ejected over a long period of time, and the quality of the recorded material obtained by the inkjet method can be stably improved. In addition, the styrene-maleic acid-based dispersant is a component that is unlikely to cause an adverse effect on the quality of recorded materials and an adverse effect on sublimation printing.

As described above, the styrene maleic acid-based dispersant may have a counterion constituting a salt, and as the counterion, for example, a divalent or higher valent ion such as an alkaline earth metal ion is used. It may be a monovalent ion, but it is preferable that it is a monovalent ion.
Examples of the monovalent ion include ammonium, amines, alkali metals and the like.

The n may be an integer of 1 or more, but is preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.

As a result, the storage stability of the aqueous inkjet composition is further improved, and the generation of foreign substances during long-term storage or the like is more effectively prevented.

As described above, one of R ¹ and R ² is-(CH ₂ CH ₂ O) _n R ³ (where R ³ is H, CH ₃ or C ₂ H ₅ and n is 1 or more. (), -CH ₂ CH (CH ₃ ) ₂ or-(CH ₂ ) ₃ CH ₃ , the other is -H,-(CH ₂ CH ₂ O) _n R ³ (where R ³ ). Is H, CH ₃ or C ₂ H ₅ , where n is an integer greater than or equal to 1), -CH ₂ CH (CH ₃ ) ₂ ,-(CH ₂ ) ₃ CH ₃ or the counterion constituting the salt. However, it is preferable that one is −CH ₂ CH (CH ₃ ) ₂ and the other is −H.

As a result, C.I. I. The dispersion stability of Nozzle Red 60 in the aqueous inkjet composition and the storage stability of the aqueous inkjet composition can be further improved, and the remarkable generation of foreign substances due to long-term storage and the ejection by the inkjet method can be achieved. It is possible to more effectively prevent the occurrence of clogging of the head filter and the nozzle at the time. As a result, the composition for water-based inkjet can be more stably discharged over a long period of time, and the quality of the recorded material by the inkjet method can be made more stable and excellent.

Further, as described above, the ratio of x and y may be any one that satisfies the relationship that y is 0.2 or more and 1.0 or less when x is 1, but y is when x is 1. The value is preferably 0.3 or more and 1.0 or less, and more preferably 0.4 or more and 1.0 or less.

As a result, C.I. I. For the dispersion stability of Disperse Red 60, the ratio of the hydrophilic group to the hydrophobic group becomes more suitable, and the long-term stability of the aqueous inkjet composition becomes further excellent.

The weight average molecular weight Mw of the styrene-maleic acid-based dispersant is not particularly limited, but is preferably 7,000 or more and 20,000 or less, more preferably 8,000 or more and 18,000 or less, and further preferably 10,000 or more and 15,000 or less. ..

As a result, the storage stability of the aqueous inkjet composition is further improved, and the generation of foreign substances during long-term storage or the like is more effectively prevented.

The aqueous inkjet composition may contain two or more compounds represented by the above general formula (1).

The content of the styrene maleic acid-based dispersant represented by the formula (1) in the aqueous inkjet composition is preferably 0.1% by mass or more and 30% by mass or less, and 1.0% by mass or more and 25% by mass or less. It is more preferably 2.0% by mass or more and 20% by mass or less.

As a result, the storage stability of the aqueous inkjet composition is further improved, and the generation of foreign substances during long-term storage or the like is more effectively prevented.

In particular, when the aqueous inkjet composition is the ink itself ejected by the inkjet method, the content of the styrene maleic acid-based dispersant represented by the formula (1) in the ink is 0.1% by mass or more and 10% by mass. % Or more, more preferably 1.0% by mass or more and 9.0% by mass or less, and further preferably 2.0% by mass or more and 8.0% by mass or less.

When the aqueous inkjet composition is a stock solution used for preparing an ink ejected by an inkjet method, the content of the styrene maleic acid-based dispersant represented by the formula (1) in the stock solution is 1.0. It is preferably 0% by mass or more and 30% by mass or less, more preferably 2.0% by mass or more and 25% by mass or less, and further preferably 5.0% by mass or more and 20% by mass or less.

When the aqueous inkjet composition contains two or more compounds represented by the general formula (1), the total content of these multiple compounds is adopted as the content.

[C. I. Disperse Red 60]
The composition for water-based inkjet is used as a disperse dye in C.I. I. Includes Disperse Red 60.

C.I. in the aqueous inkjet composition. I. The content of Disperse Red 60 is preferably 0.1% by mass or more and 30% by mass or less, more preferably 2.0% by mass or more and 25% by mass or less, and 5.0% by mass or more and 20% by mass or less. The following is more preferable.

As a result, a higher color density can be obtained in the recording unit formed by using the water-based inkjet composition, the storage stability of the water-based inkjet composition is further improved, and foreign substances are generated during long-term storage or the like. Is prevented more effectively.

Further, in the composition for water-based inkjet, C.I. I. When the content of Disperse Red 60 is XD [mass%] and the content of the styrene maleic acid-based dispersant is XM [mass%], it is preferable to satisfy the relationship of 0.04 ≤ XM / XD ≤ 25. It is more preferable to satisfy the relationship of 0.1 ≦ XM / XD ≦ 5.0, and further preferably to satisfy the relationship of 0.35 ≦ XM / XD ≦ 1.3.

As a result, the storage stability of the aqueous inkjet composition is further improved, and the generation of foreign substances during long-term storage or the like is more effectively prevented.

C.I. in the aqueous inkjet composition. I. The average particle size of Disperse Red 60 is preferably 50 nm or more and 300 nm or less, more preferably 75 nm or more and 250 nm or less, and further preferably 100 nm or more and 200 nm or less.

As a result, the storage stability of the aqueous inkjet composition is further improved, and the generation of foreign substances during long-term storage or the like is more effectively prevented. In addition, the recording unit formed by using the aqueous inkjet composition can be sublimated more effectively, and can be more preferably applied by sublimation printing.

In the present specification, the average particle size refers to the volume-based average particle size unless otherwise specified. The average particle size can be determined, for example, by measurement using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

C. I. Examples of commercially available products of Disperse Red 60 include plastread 8375 (manufactured by Arimoto Chemical Industry Co., Ltd.) and the like.

[water]
The composition for an aqueous inkjet contains water.
The content of water in the aqueous inkjet composition is not particularly limited, but is preferably 30% by mass or more and 85% by mass or less, more preferably 35% by mass or more and 80% by mass or less, and 40% by mass. It is more preferably 75% by mass or less.

Thereby, the viscosity of the aqueous inkjet composition can be more reliably adjusted to a suitable value, and the ejection stability by the inkjet method can be further improved.

[Solvents other than water]
The composition for water-based inkjet may contain a solvent other than water.

Thereby, the viscosity of the aqueous inkjet composition can be suitably adjusted, and the moisturizing property of the aqueous inkjet composition can be enhanced. As a result, the droplet ejection by the inkjet method can be performed more stably.

Examples of the solvent other than water contained in the aqueous inkjet composition include glycerin, propylene glycol, 2-pyrrolidone and the like.

By containing these solvents, the evaporation rate can be slowed down due to the excellent moisturizing ability, and more stable droplet ejection can be performed.

The content of the solvent other than water contained in the aqueous inkjet composition is preferably 0% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 43% by mass or less, and 15% by mass. It is more preferably 40% by mass or less.
As a result, the effect of containing a solvent other than the above-mentioned water is more remarkable.

[Surfactant]
The composition for aqueous inkjet may contain a surfactant.

As a result, the wettability of the aqueous inkjet composition with respect to the recording medium (base material) can be made more suitable, which is advantageous in obtaining better image quality.

As the surfactant contained in the aqueous inkjet composition, for example, various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used.

More specifically, examples of the surfactant contained in the aqueous inkjet composition include acetylene-based surfactants, silicone-based surfactants, and fluorine-based surfactants.

When the water-based inkjet composition contains an acetylene-based surfactant, the dynamic surface tension of the water-based inkjet composition can be suitably lowered, and the meniscus can be quickly oriented. As a result, the ejection stability by the inkjet method can be made more excellent.

When the composition for water-based inkjet contains an acetylene-based surfactant, the content of the acetylene-based surfactant in the composition for water-based inkjet is determined by C.I. I. Disperse Red 60: It is preferably 5.0 parts by mass or more and 75 parts by mass or less, more preferably 6.0 parts by mass or more and 50 parts by mass or less, and 7.0 parts by mass or more with respect to 100 parts by mass. It is more preferably 30 parts by mass or less.

As a result, the effect of containing the above-mentioned acetylene-based surfactant is more remarkable.

Examples of commercially available acetylene-based surfactants include Orfin E1004, Orfin E1010, Orfin E1020, Orfin PD-001, Orfin PD-002W, Orfin PD-004, Orfin PD-005, Orfin EXP4001, Orfin EXP4200, Orfin EXP4123, and others. Examples thereof include Orfin EXP4300, Orfin WE-001, and Orfin WE-003 (all of which are manufactured by Nisshin Kagaku Kogyo Co., Ltd.).

[Other ingredients]
The composition for water-based inkjet may contain components (other components) other than the above-mentioned components.

Other components include, for example, C.I. I. Colorants other than Disperse Red 60, dispersants other than the above-mentioned styrene maleic acid-based dispersants, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol monomethyl ether, 1,2-hexanediol, 1,2-pentanediol , 1,2-butanediol, 3-methyl 1,5-pentanediol and other penetrants, pH adjusters, ethylenediamine tetraacetate (EDTA) and other chelating agents, preservatives / antifungal agents, rust preventives, etc. Can be mentioned. As the preservative / fungicide, for example, a compound having an isothiazolin ring structure in the molecule can be preferably used.

The content of other components (when a plurality of types of components are contained as other components, the total content of these components) is preferably 6% by mass or less, and more preferably 5% by mass or less.

In particular, when the aqueous inkjet composition of the present invention contains a dispersant (other dispersant) other than the above-mentioned styrene maleic acid-based dispersant, the content of the dispersant (other dispersant) is 5% by mass. % Or less, more preferably 3% by mass or less.

The surface tension of the aqueous inkjet composition at 25 ° C. is preferably 20 mN / m or more and 50 mN / m or less, more preferably 21 mN / m or more and 40 mN / m or less, and 23 mN / m or more and 30 mN / m or less. Is more preferable.

As a result, clogging of the nozzle of the ejection device by the inkjet method is less likely to occur, and the ejection stability of the aqueous inkjet composition is further improved. Further, even if the nozzle is clogged, the recoverability by capping the nozzle (capping) can be further improved.

As the surface tension, a value measured by the Wilhelmy method can be adopted. A surface tension meter (for example, manufactured by Kyowa Interface Science Co., Ltd., CBVP-7, etc.) can be used for measuring the surface tension.

The viscosity of the aqueous inkjet composition at 25 ° C. is preferably 2 mPa · s or more and 30 mPa · s or less, more preferably 3 mPa · s or more and 20 mPa · s or less, and 4 mPa · s or more and 10 mPa · s or less. It is even more preferable to have it.
This further improves the ejection stability of the aqueous inkjet composition.

The viscosity was increased from 10 [s ^-1 ] to 1000 [s ^-1 ] using a viscoelasticity tester (for example, MCR-300 manufactured by Pysica) at 25 ° C. It can be measured by reading the viscosity at Shear Rate 200.

The aqueous inkjet composition of the present invention is usually applied to a recording device by an inkjet method in a state of being stored in a container such as a cartridge, a bag, or a tank. In other words, the recording device according to the present invention includes a container (ink cartridge or the like) for storing the aqueous inkjet composition of the present invention.

The aqueous inkjet composition of the present invention may be an ink ejected by an inkjet method or a stock solution used for preparing the ink, and the specific configuration of the device for ejecting droplets is not limited, but the aqueous composition of the present invention is limited. The composition for inkjet includes an ink jet recording device (more specifically, for example, an ink containing container provided with an ink injection port capable of replenishing ink, and a recording head having a nozzle hole for ejecting the ink). It is preferably the one that is applied to the recording device (including the undiluted solution).

In such a recording device, C.I. I. When an ink containing Disperse Red 60 is applied, there is a problem that foreign matter (particularly crystalline foreign matter) is particularly likely to be generated at the gas-liquid interface due to the ink coming into contact with the atmosphere. According to this, even when applied to such a recording device, it is possible to effectively prevent the occurrence of the above-mentioned problems. That is, the effect of the present invention is more remarkably exhibited when it is applied to an open-air recording device.

<Recording method>
The composition for water-based inkjet of the present invention can be applied to, for example, a direct printing method, a thermal transfer printing method (for example, sublimation printing), and the like. I. Since the Disperse Red 60 has sublimation properties, it can be suitably applied to the thermal transfer printing method.

Hereinafter, an example of a thermal transfer printing method (sublimation printing) will be described as a recording method using the aqueous inkjet composition of the present invention.

The recording method according to the present embodiment is an ink adhesion step of adhering an aqueous inkjet composition to an intermediate transfer medium by an inkjet method, and heating the intermediate transfer medium to which the aqueous inkjet composition is attached to form an aqueous inkjet composition. C.I. as a sublimation dye contained in a product. I. It has a transfer step of transferring the Disperse Red 60 to a recording medium.

[Ink adhesion process]
In the ink adhesion step, the aqueous inkjet composition is adhered to the intermediate transfer medium by an inkjet method. The water-based inkjet composition can be ejected by an inkjet method using a known inkjet recording device. As the ejection method, a piezo method, a method of ejecting ink by bubbles generated by heating the ink, or the like can be used. Above all, the piezo method is preferable from the viewpoint of difficulty in deteriorating the composition for water-based inkjet.

In the ink adhesion step, inks other than the aqueous inkjet composition according to the present invention may be used in combination.

[Intermediate transfer medium]
As the intermediate transfer medium, for example, paper such as plain paper, a recording medium provided with an ink receiving layer (referred to as inkjet paper, coated paper, or the like) or the like can be used. Of these, paper provided with an ink receiving layer made of inorganic fine particles such as silica is preferable. As a result, an intermediate transfer medium in which bleeding and the like are suppressed can be obtained in the process of drying the aqueous inkjet composition adhering to the intermediate transfer medium, and in a later transfer step, C.I. I. The sublimation of Disperse Red 60 tends to proceed more smoothly.

[Transfer process]
Then, the intermediate transfer medium to which the aqueous inkjet composition is attached is heated, and C.I. I. The Disperse Red 60 is transferred to a recording medium. As a result, a recorded material is obtained.

The heating temperature in this step is preferably 160 ° C. or higher and 220 ° C. or lower, and more preferably 170 ° C. or higher and 200 ° C. or lower.

As a result, the energy required for transcription can be reduced, and the productivity of the recorded material can be further improved. In addition, the color development of the obtained recorded material can be further improved.

The heating time in this step is preferably 30 seconds or more and 90 seconds or less, and more preferably 45 seconds or more and 80 seconds or less, although it depends on the heating temperature.

As a result, the energy required for transcription can be reduced, and the productivity of the recorded material can be further improved. In addition, the color development of the obtained recorded material can be further improved.

Further, this step may be performed by heating the surface of the intermediate transfer medium to which the aqueous inkjet composition is attached in a state of facing the recording medium at regular intervals, or by heating the surface of the recording medium. Although it may be carried out by heating in a state of being in close contact with the surface, it is preferably carried out by heating the surface of the intermediate transfer medium to which the aqueous inkjet composition is attached in a state of being in close contact with the surface of the recording medium.

As a result, the energy required for transcription can be reduced, and the productivity of the recorded material can be further improved. In addition, the color development of the obtained recorded material can be further improved.

[recoding media]
The recording medium is not particularly limited, and examples thereof include cloth (hydrophobic fiber cloth and the like), resin (plastic) film, paper, glass, metal, ceramics and the like. Further, as the recording medium, a material having a three-dimensional shape such as a sheet shape, a spherical shape, or a rectangular parallelepiped shape may be used.

When the recording medium is a cloth, examples of the fibers constituting the cloth include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended products using two or more of these fibers. .. Further, a blended product of these with recycled fibers such as rayon or natural fibers such as cotton, silk and wool may be used.

When the recording medium is a resin (plastic) film, examples of the resin (plastic) film include a polyester film, a polyurethane film, a polycarbonate film, a polyphenylene sulfide film, a polyimide film, and a polyamideimide film.

The resin (plastic) film may be a laminated body in which a plurality of layers are laminated, or may be composed of a functionally graded material whose composition of the material changes in an inclined manner.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto.

For example, the aqueous inkjet composition of the present invention may be any one used for ejection by an inkjet method, and may not be applied to the recording method as described above.

For example, it may be applied to a method having other steps (pretreatment step, intermediate treatment step, posttreatment step) in addition to the steps as described above.

In this case, examples of the pretreatment step include a step of applying a coat layer to a recording medium.

In addition, examples of the intermediate treatment step include a step of preheating the recording medium.
In addition, examples of the post-treatment step include a step of cleaning the recording medium.

Further, the aqueous inkjet composition of the present invention can be suitably applied to sublimation transfer without using an intermediate transfer medium. Sublimation transfer without using an intermediate transfer medium includes, for example, a step of adhering an aqueous ink jet composition to an ink receiving layer of a recording medium (film product or the like) provided with a peelable ink receiving layer by an inkjet method. The step of heating the recording medium provided with the ink receiving layer to which the water-based inkjet composition is attached as it is, sublimating and diffusing dyeing from the ink receiving layer to the recording medium on the lower layer side, and peeling the ink receiving layer from the recording medium. Examples thereof include a method having a step of obtaining a recorded material.

Next, specific examples of the present invention will be described.
[1] Preparation of undiluted solution for inkjet ink production (composition for aqueous inkjet)

(Example A1)
First, C.I. as a disperse dye. I. Disperse Red 60 and the styrene maleic acid-based dispersant represented by the above formula (1) (however, one of R ¹ and R ² in the formula (1) is −H, and the other is −CH ₂ CH (CH ₃ ). _2. A compound having a relationship of 1 when x is 1 and a weight average molecular weight Mw of 13000) and pure water are mixed at the ratios shown in Table 2 and mixed with a high shear mixer (manufactured by Silberson). ) Was stirred at 3000 rpm to form a slurry. Then, the produced slurry and 0.5 mm diameter glass beads were stirred and dispersed under water cooling in a bead mill (LMZ015 Ashizawa Finetech Co., Ltd.) to produce an undiluted solution for producing an inkjet ink as an aqueous inkjet composition.
C.I. in the undiluted solution for manufacturing inkjet ink. I. The average particle size of Disperse Red 60 was 150 nm.

(Examples A2-A21)
A stock solution for producing an inkjet ink as an aqueous inkjet composition is prepared in the same manner as in Example A1 except that the chemical structure of the styrene-maleic acid-based dispersant and the compounding ratio of each component are shown in Tables 1 and 2. Manufactured.

(Comparative Examples A1 to A9)
A stock solution for producing an inkjet ink as an aqueous inkjet composition is prepared in the same manner as in Example A1 except that the types of disperse dyes, the types of dispersants, and the blending ratios of each component are shown in Tables 1 and 2. Manufactured.

Table 1 shows the relationship between the abbreviations of the dispersants used in the preparation of the aqueous inkjet composition (stock solution for manufacturing inkjet ink) of each of the above-mentioned Examples and Comparative Examples and the conditions, and of each of the above-mentioned Examples and Comparative Examples. Table 2 shows the composition of the aqueous inkjet composition (undiluted solution for producing inkjet ink). In the table, C.I. I. Disperse Red 60 is referred to as "DR60", C.I. I. Disperse Red 153 is referred to as "DR153", C.I. I. Disperse Red 167 is "DR167", J-67 (manufactured by BASF) as a dispersant other than styrene maleic acid dispersant is "H6", and X310 (Seikou PMC) as a dispersant other than styrene maleic acid dispersant. (Manufactured) is indicated as "H7". The undiluted solutions for manufacturing inkjet inks of Examples A1 to A21 all have a viscosity in the range of 2.0 mPa · s or more and 30 mPa · s or less, and a surface tension of 25 mN / m or more and 50 mN / m or less. It was a value within the range of. The viscosity of the Shear Rate was increased from 10 [s ^-1 ] to 1000 [s ^-1 ] at 25 ° C. using a viscoelasticity tester MCR-300 (manufactured by Pysica). It was measured by reading the viscosity of the hour. The surface tension was measured by the Wilhelmy method at 25 ° C. using a surface tension meter (CBVP-7, manufactured by Kyowa Interface Science Co., Ltd.).

[2] Evaluation of undiluted solution for manufacturing inkjet ink [2-1] Storage stability (change in particle size)
For each of the above-mentioned Examples and Comparative Examples of the aqueous inkjet composition (undiluted solution for producing inkjet ink), the average particle size of the disperse dye immediately after production and the average particle size of the disperse dye immediately after production were placed in a predetermined container and left in an environment of 60 ° C. for 1 week. The average particle size of the disperse dye was obtained, and from these values, the fluctuation rate of the average particle size of the disperse dye when left in an environment of 60 ° C. for one week with respect to the average particle size of the disperse dye immediately after production was obtained. , Evaluated according to the following criteria. A Microtrac UPA (manufactured by Nikkiso Co., Ltd.) was used for measuring the average particle size.

A: The volatility of the average particle size is less than 3%.
B: The volatility of the average particle size is 3% or more and less than 5%.
C: The volatility of the average particle size is 5% or more and less than 7%.
D: The volatility of the average particle size is 7% or more and less than 10%.
E: The volatility of the average particle size is 10% or more.

[2-2] Status of generation of foreign substances 10 mL of each of the aqueous inkjet compositions (undiluted solution for inkjet ink production) of each of the above Examples and Comparative Examples is placed in a predetermined glass bottle, and a gas-liquid interface is present. Then, it was left in an environment of 60 ° C. for 5 days. Then, the aqueous inkjet composition (stock solution for inkjet ink production) is filtered through a metal mesh filter (diameter 10 μm), the number of solids remaining on the metal mesh filter per 1 mm square is counted, and the number is according to the following criteria. evaluated.

A: The number of solids per 1 mm square was less than 5.
B: The number of solids per 1 mm square was 5 or more and less than 20.
C: The number of solids per 1 mm square was 20 or more and less than 30.
D: The number of solids per 1 mm square was 30 or more and less than 50.
E: The number of solids per 1 mm square was 50 or more.
These results are summarized in Table 3.

As is clear from Table 3, excellent results were obtained in the present invention. On the other hand, in the comparative example, satisfactory results were not obtained.

[3] Preparation of Inkjet Ink (Aqueous Inkjet Composition) (Example B1)
The stock solution for inkjet ink production prepared in Example A1, glycerin, 2-pyrrolidone, propylene glycol, Orfin EXP4300 (manufactured by Nisshin Chemical Industry Co., Ltd.) as an acetylene-based surfactant, and pure water are shown. Inkjet ink as an aqueous inkjet composition was produced by mixing at the ratio shown in 4 and stirring at 3000 rpm with a high shear mixer (manufactured by Silberson).

C. in inkjet ink. I. The average particle size of Disperse Red 60 was 150 nm.

(Examples B2 to B25)
The types of undiluted solutions for manufacturing inkjet ink are shown in Tables 4 and 5, and the compounding ratios of the respective components are shown in Tables 4 and 5, except that they are for water-based inkjet in the same manner as in Example B1. Inkjet ink as a composition was produced.

(Comparative Examples B1 to B9)
Inkjet ink as an aqueous inkjet composition in the same manner as in Example B1 except that the types of undiluted solutions for producing inkjet ink are shown in Table 5 and the compounding ratio of each component is shown in Table 5. Manufactured.

The conditions of the aqueous inkjet composition (inkjet ink) of each of the Examples and Comparative Examples are summarized in Tables 4 and 5. In the table, glycerin is "Gly", 2-pyrrolidone is "2-Py", propylene glycol is "PG", BYK348 (manufactured by Big Chemie Japan) as a silicone-based surfactant is "BYK348", and acetylene-based. Orphine EXP4300 (manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant is referred to as "EXP4300". Further, all of the inkjet inks of Examples B1 to B25 have a viscosity in the range of 2.0 mPa · s or more and 10.0 mPa · s or less, and a surface tension of 20 mN / m or more and 35 mN / m or less. The value was within the range. The viscosity of the Shear Rate was increased from 10 [s ^-1 ] to 1000 [s ^-1 ] at 25 ° C. using a viscoelasticity tester MCR-300 (manufactured by Pysica). It was measured by reading the viscosity of the hour. The surface tension was measured by the Wilhelmy method at 25 ° C. using a surface tension meter (CBVP-7, manufactured by Kyowa Interface Science Co., Ltd.).

[4] Evaluation of inkjet ink [4-1] Storage stability (change in particle size)
For the aqueous ink composition (inkjet ink) of each of the above Examples and Comparative Examples, the average particle size of the disperse dye immediately after production and the case where they were placed in a predetermined ink storage container and left in an environment of 60 ° C. for one week. From these values, the fluctuation rate of the average particle size of the disperse dye when left in an environment of 60 ° C. for one week was obtained with respect to the average particle size of the disperse dye immediately after production. The evaluation was made according to the following criteria. A Microtrac UPA (manufactured by Nikkiso Co., Ltd.) was used for measuring the average particle size.

A: The volatility of the average particle size is less than 3%.
B: The volatility of the average particle size is 3% or more and less than 5%.
C: The volatility of the average particle size is 5% or more and less than 7%.
D: The volatility of the average particle size is 7% or more and less than 10%.
E: The volatility of the average particle size is 10% or more.

[4-2] Occurrence of Foreign Substances Only 10 mL of the aqueous inkjet composition (inkjet ink) of each of the above-mentioned Examples and Comparative Examples is placed in a predetermined glass bottle, and 60 in a state where a gas-liquid interface is present. It was left in an environment of ℃ for 5 days. Then, the aqueous inkjet composition (inkjet ink) was filtered through a metal mesh filter (diameter 10 μm), the number of solids remaining on the metal mesh filter per 1 mm square was counted, and the evaluation was made according to the following criteria.

A: The number of solids per 1 mm square was less than 5.
B: The number of solids per 1 mm square was 5 or more and less than 20.
C: The number of solids per 1 mm square was 20 or more and less than 30.
D: The number of solids per 1 mm square was 30 or more and less than 50.
E: The number of solids per 1 mm square was 50 or more.

[4-3] Discharge stability by inkjet method The aqueous inkjet compositions (inkjet inks) of the above-mentioned Examples and Comparative Examples are each filled in a predetermined ink container and left in an environment of 60 ° C. for 5 days. did.

After that, the storage container is attached to a recording device PX-H6000 (manufactured by Seiko Epson), inkjet ink is ejected, and the intermediate transfer medium TRANSJET Classic (manufactured by Cham Paper) is solid with a recording resolution of 1440 × 720 dpi. The pattern was attached. The operating environment of the recording device (printer) was set to 40 ° C. and 20 RH%.

The number of missing nozzles when 30 solid patterns were recorded on the intermediate transfer medium was examined and evaluated according to the following criteria.

A: The number of missing nozzles was 0.
B: The number of missing nozzles was 1 or more and 9 or less.
C: The number of missing nozzles was 10 or more and 19 or less.
D: The number of missing nozzles was 20 or more and 29 or less.
E: The number of missing nozzles was 30 or more.

The ink container of PX-H6000 manufactured by Seiko Epson (the above-mentioned ink container) is provided with an ink injection port capable of replenishing the water-based inkjet composition, and when attached to a recording device in a used state, it is provided. It is open to the atmosphere.

[4-4] Color development (OD value)
The adhesion side of the aqueous inkjet composition of the 30th intermediate transfer medium to which the inkjet ink was adhered in [4-3] is brought into close contact with a cloth (100% polyester, manufactured by Amina, Toray Industries, Inc.) which is a white recording medium. In this state, using a heat press machine (TP-608M, manufactured by Taiyo Seiki Co., Ltd.), the mixture was heated at 180 ° C. for 60 seconds and sublimation transfer was performed to obtain each recorded matter.

The color development was evaluated for each of the obtained recorded materials. Specifically, the OD value of each of the obtained recorded materials was measured using a colorimeter (Gretag Macbeth Spectralino, manufactured by X-Rite) and evaluated according to the following criteria.

A: The OD value is 1.50 or more.
B: The OD value is 1.45 or more and less than 1.50.
C: The OD value is 1.40 or more and less than 1.45.
D: The OD value is 1.35 or more and less than 1.40.
E: The OD value is less than 1.35.
These results are summarized in Tables 6 and 7.

As is clear from Tables 6 and 7, excellent results were obtained in the present invention. On the other hand, in the comparative example, satisfactory results were not obtained.

Claims (8)

C. I. Disperse Red 60 and
An aqueous inkjet composition comprising a styrene-maleic acid-based dispersant represented by the following formula (1).

(In the formula (1), one of R ¹ and R ² is-(CH ₂ CH ₂ O) _n R ³ (where R ³ is H, CH ₃ or C ₂ H ₅ and n is. It is an integer of 1 or more.) Or -CH ₂ CH (CH ₃ ) ₂ , the other is -H, and x and y are 0.2 or more and 1.0 or less when x is 1. It is a relationship that becomes.) The C.I. I. Claim 1 that satisfies the relationship of 0.04 ≤ XM / XD ≤ 25 when the content of Disperse Red 60 is XD [mass%] and the content of the styrene maleic acid-based dispersant is XM [mass%]. The composition for aqueous inkjet according to. The C.I. I. The aqueous inkjet composition according to claim 1 or 2, wherein the content of Disperse Red 60 is 0.1% by mass or more and 30% by mass or less. The aqueous inkjet composition according to any one of claims 1 to 3, wherein the content of the styrene-maleic acid-based dispersant is 0.1% by mass or more and 30% by mass or less. The aqueous inkjet composition according to any one of claims 1 to 4, wherein the styrene-maleic acid-based dispersant has a weight average molecular weight of 7,000 or more and 20,000 or less. It further contains an acetylene-based surfactant, and the content of the acetylene-based surfactant is the above-mentioned C.I. I. Disperse Red 60: The aqueous inkjet composition according to any one of claims 1 to 5, wherein the composition is 5.0 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass. The aqueous inkjet composition according to any one of claims 1 to 6, wherein the surface tension at 25 ° C. is 20 mN / m or more and 50 mN / m or less. The aqueous inkjet composition according to any one of claims 1 to 7, wherein the viscosity at 25 ° C. is 2 mPa · s or more and 30 mPa · s or less.