JP2017088846A - Ink, ink accommodation container, inkjet recording method, inkjet recording device and recorded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink capable of forming an image good in scratch resistance and excellent in discharge stability and storage stability.SOLUTION: There is provided an ink containing an organic solvent, water, a coloring material, a wax and a resin particle, containing an acrylic resin particle and an urethane resin particle as the resin particle and having mass ratio of content of the urethane resin particle (mass%) and content of the acrylic resin particle (mass%) (urethane resin particle/acrylic resin particle) of 0.1 to 0.7. The wax preferably has a form of polyethylene wax and the urethane resin particle preferably has a form of a polycarbonate urethane resin particle.SELECTED DRAWING: None

Description

  The present invention relates to an ink, an ink container, an ink jet recording method, an ink jet recording apparatus, and a recorded matter.

  Compared to other recording systems, the inkjet recording system is simpler in process, easier to achieve full color, and can be used for personal and office applications because even high-resolution images can be obtained even with a simple configuration. It is spreading into the fields of commercial printing and industrial printing.

  In the field of commercial printing, coated paper such as coated paper or art paper is used as a recording medium in addition to plain paper, and the printed matter is handled as a product such as a postcard or package, so that the image has high resistance to images. Abrasion is required. In addition, printing down time is reduced, and high productivity is required. In the ink jet recording method, ejection stability is required. However, the ink having scratch resistance tends to cause ink sticking at the recording head portion, and it is difficult to achieve both scratch resistance and ejection stability.

  Therefore, it contains a water-insoluble colorant, resin particles, silicone surfactant, acetylene glycol surfactant, pyrrolidone derivative, 1,2-alkyldiol, polyhydric alcohol, and water. An ink jet recording printing method using an aqueous ink composition containing fixing particles and wax particles has been proposed (see, for example, Patent Document 1).

  An object of the present invention is to provide an ink that can form an image having good scratch resistance and is excellent in ejection stability and storage stability.

  The ink of the present invention as a means for solving the problems is an ink containing an organic solvent, water, a coloring material, wax, and resin particles, and the resin particles include acrylic resin particles and urethane resin particles. And the mass ratio (urethane resin particles / acrylic resin particles) between the content (mass%) of the urethane resin particles and the content (mass%) of the acrylic resin particles is 0.1 or more and 0.7 or less. is there.

  According to the present invention, it is possible to provide an ink excellent in ejection stability and storage stability while being able to form an image having good scratch resistance.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of a main tank of the apparatus of FIG. FIG. 3 is a schematic diagram showing the area A of the peak region and the area B of the peak region.

The ink of the present invention is an ink containing an organic solvent, water, a coloring material, wax, and resin particles, and includes acrylic resin particles and urethane resin particles as the resin particles, and the content of the urethane resin particles ( % By mass) and the content (% by mass) of the acrylic resin particles (urethane resin particles / acrylic resin particles) are 0.1 or more and 0.7 or less, and if necessary, other Contains ingredients.
The ink of the present invention is based on the knowledge that it is difficult for conventional inks to satisfy all of scratch resistance, ejection stability, and storage stability.

In addition, the present inventors have obtained the following knowledge.
The ink containing the acrylic resin particles is excellent in ejection stability, but the acrylic resin particles have high hardness and low elasticity, and thus the resulting image tends to have low scratch resistance. In contrast, inks containing urethane resin particles tend to have higher scratch resistance of the resulting image because the urethane resin particles have lower hardness and higher elasticity than acrylic resin particles. Therefore, it is expected that the ink containing acrylic resin particles and urethane resin particles improves the scratch resistance while ensuring the ejection stability.
However, the ink containing urethane resin particles has a strong hydrogen bonding force, so it is easy to form a film, and a sticking matter is easily generated in the recording head portion, and the discharge stability tends to be inferior due to the sticking matter. In order to prevent the occurrence of fixed matter, the content of urethane resin particles cannot be increased, and the resulting image cannot sufficiently satisfy the scratch resistance.
It is also known that although the mechanical strength of the obtained image can be improved, the dynamic friction coefficient of the image is increased.
Therefore, by including acrylic resin particles and urethane resin particles in a specific mass ratio, and further containing wax, the dynamic friction coefficient of the obtained image can be reduced, and even if the content of urethane resin particles is small, scratch resistance is achieved. Was found to be good and excellent in ejection stability and storage stability.

Further, the ink includes an organic solvent, water, a coloring material, wax, and resin particles, and the resin particles include acrylic resin particles and urethane resin particles, and the content (% by mass) of the urethane resin particles The ink film formed using the ink of the present invention having a mass ratio (urethane resin particles / acrylic resin particles) to the content (% by mass) of the acrylic resin particles of 0.1 or more and 0.7 or less, when measured by Fourier transform infrared absorption spectroscopy, from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the minimum point and spectrum 660 cm ^-1 or more 690 cm ^-1 or less in between: spectrum 710 cm ^-1 or more 740 cm ^-1 the tangent line connecting the minimum points between, by the area of the peak area a surrounded, and 1,750cm from the spectrum 1,731Cm ^-1 They surrounded a region of up to ^1, the tangent line connecting the minimum point between the minimum point and spectral 1,760Cm ^-1 or more 1,790Cm ^-1 or less between the following spectral 1,660Cm ^-1 or 1,690Cm ^-1, by The area ratio (B / A) of the area B of the peak region is 0.3 or more and 1.0 or less, and the dynamic friction coefficient of the ink film in which the ink adhesion amount is 1.12 mg / cm ² is 0. 4 or less.

<Ink>
Hereinafter, the organic solvent, water, color material, resin, additive, and the like used for the ink will be described.

<Resin particles>
The resin particles contain acrylic resin particles and urethane resin particles, and further contain other resin particles as necessary.

The resin particles are preferably water-dispersible dispersions, for example.
Examples of the acrylic resin particles include acrylic silicone resin particles and styrene acrylic resin particles. These may be used individually by 1 type and may use 2 or more types together. Among these, acrylic silicone resin particles are preferable from the viewpoint of scratch resistance.
Examples of the urethane resin particles include polycarbonate urethane resin particles, polyester urethane resin particles, and polyether urethane resin particles. These may be used individually by 1 type and may use 2 or more types together. Among these, polycarbonate urethane resin particles are preferable from the viewpoint of scratch resistance and storage stability. In addition, the said polycarbonate urethane resin particle should just have a polycarbonate structure in the structure, and is the meaning also including a polycarbonate-type urethane resin particle.

  As the resin particles, commercially available products or synthetic products may be used. Examples of the commercially available products include acrylic resin particles as trade names: Saimak (manufactured by Toagosei Co., Ltd.), trade names: Boncoat. (Made by DIC Corporation) Aquabrid (made by Daicel Corporation); Urethane resin particles as trade name: U-coat (Daiichi Kogyo Seiyaku Co., Ltd.), trade name: Takerak (made by Mitsui Chemicals), polycarbonate urethane resin particles Product name: Takerak W-4000, Product name: Takerak W-6010, Product name: Takerak W-6110 (Mitsui Chemicals, Inc.) and the like. These may be used individually by 1 type and may use 2 or more types together.

The Martens hardness of the resin particles is preferably 10 N / mm ² or less from the viewpoint of scratch resistance.
Examples of the Martens hardness of the urethane resin particles, from the viewpoint of abrasion resistance, preferably from 10 N / mm ² or less, 0.1 N / mm ² or more 10 N / mm ² or less being more preferred.
As the Martens hardness, a resin particle solution is coated on a support such as a slide glass (trade name: white plate glass S111, manufactured by Matsunami Glass Industrial Co., Ltd.) so as to have an average thickness of 10 μm or more, and at 60 ° C. After pre-drying for 3 hours, the resin film is obtained by drying at 100 ° C. for 6 hours. Using a micro hardness tester (device name: HM-2000, manufactured by Fischer Instruments Co., Ltd.), the Vickers indenter was pushed in with a force of 1.0 mN for 10 seconds and held for 5 seconds. It can be measured by pulling out in 10 seconds with a force of 1.0 mN.

The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of improving the image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number is converted. Is preferably 20 nm to 1000 nm, and more preferably 20 nm to 150 nm. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The content of the resin particles is preferably 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 25% by mass or less with respect to the total amount of the ink.

The content of the acrylic resin particles is preferably 5% by mass or more and 30% by mass or less, and more preferably 6% by mass or more and 20% by mass or less with respect to the total amount of the ink.
The content of the urethane resin particles is preferably 1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 4% by mass or less with respect to the total amount of the ink.

[Mass ratio (urethane resin particles / acrylic resin particles)]
The mass ratio (urethane resin particles / acrylic resin particles) between the content (% by mass) of the urethane resin particles and the content (% by mass) of the acrylic resin particles is 0.1 or more and 0.7 or less. In view of scratch resistance, ejection stability, and storage stability, 0.4 or more and 0.7 or less are preferable.

<Wax>
The wax can reduce the coefficient of dynamic friction on the surface of the image (ink film), and in particular, when combined with urethane resin particles, the scratch resistance of the image can be dramatically improved. This can prevent the dynamic friction coefficient from being increased by the urethane resin particles contained in order to improve the scratch resistance of the image, reduce the force received by the image, and sufficiently increase the mechanical strength of the urethane resin particles. Since it is exhibited, it is estimated that the scratch resistance can be dramatically improved.

The wax is preferably a water dispersible wax emulsion.
Examples of the wax include polyethylene wax and paraffin wax. These may be used individually by 1 type and may use 2 or more types together. Among these, polyethylene wax is preferable from the viewpoint of storage stability.

  A commercially available product can be used as the wax. Examples of the commercially available product include trade name: HYTEC E-8237 (polyethylene wax, melting point: 106 ° C., average particle size: 80 nm, manufactured by Toho Chemical Industry Co., Ltd.) , Trade name: AQUACER 531 (polyethylene wax, melting point: 130 ° C., manufactured by Big Chemie), trade name: AQUACER 515 (polyethylene wax, melting point: 135 ° C., manufactured by Big Chemie), trade name: AQUACER 537 (paraffin, melting point: 110 ° C., Big Chemie) Etc.). These may be used individually by 1 type and may use 2 or more types together.

  As melting | fusing point of the said wax, 70 to 170 degreeC is preferable and 100 to 140 degreeC is more preferable. When the melting point is 70 ° C. or higher, the image is not sticky, and even when the images are overlapped, image transfer does not occur. Therefore, the scratch resistance is good.

The wax has a volume average particle size of preferably 200 nm or less, more preferably 20 nm or more and 150 nm or less. When the volume average particle size is 200 nm or less, good ejection stability can be obtained without being caught by the nozzle or the filter in the head.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  The wax content is preferably 0.09% by mass or more and 0.5% by mass or less in terms of solid content with respect to the total amount of ink. When the solid content concentration is 0.09 mass% or more and 0.5 mass% or less, there is a sufficient effect in reducing the dynamic friction coefficient on the surface of the obtained image (ink film), and the storage stability of the ink, and Does not adversely affect the discharge stability.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include ethers such as polyhydric alcohols, polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-he Polyhydric alcohols such as sundiol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, ethylene glycol mono Polyhydric alcohol alkyl ethers such as ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Polyhydric alcohol aryl ethers such as benzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl- -N-containing heterocyclic compounds such as pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, Amides such as N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate, Examples thereof include ethylene carbonate.
In addition to functioning as a wetting agent, it is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because good drying properties can be obtained.

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and the like.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Examples of ethers include polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

  A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve ink permeability when paper is used as a recording medium.

The total Hansen solubility parameter of the organic solvent as a (hereinafter, sometimes also referred to as "totHSP value") is preferably ^{20 MPa 1/2} or more ^{23 MPa 1/2} or less, 20.2 MPa ^1/2 or more 22.6MPa ^1/2 The following is more preferable. The total Hansen solubility parameter, if it is 20 MPa ^1/2 or more 23 MPa ^1/2 or less, the organic solvent is a polar close to both polarities are different compatibilization hardly acrylic resin particles and urethane resin particles, acrylic resin Compatibility with both the particles and the urethane resin particles is improved, and a uniform ink can be obtained. Moreover, a uniform dispersed state can be maintained for a long time, and the storage stability of the ink can be improved.
The totHSP value is an index representing the solubility of a substance. The totHSP value is different from the Hilde brand SP value used in Solvent Handbook (Kodansha Scientific Co., Ltd., published in 1976) and has a multi-dimensional solubility (typically three-dimensional). ) Vector. This vector can typically be expressed by a dispersion term (δD), a polarity term (δP), and a hydrogen bond term (δH), where the dispersion term (δD) is a van der Waals force and a polarity term (δP). Represents the dipole moment, and the hydrogen bond term (δH) reflects the action of water, alcohol, and the like. The totHSP value, said a sum of squares of each vector ^{((δD) 2 + (δP} ) 2 + (δH) 2).
The totHSP value can be calculated by software such as trade name: HSPiP.

The Hansen solubility parameters as the dispersion term (hereinafter, sometimes also referred to as "HSP value") ([delta] D), preferably ^{15 MPa 1/2} or more ^{18 MPa 1/2} or less.
As the HSP value of polarity term ([delta] P), preferably ^{6 MPa 1/2} or ^{14 MPa 1/2} or less, ^{6 MPa 1/2} or ^{11 MPa 1/2} or less is more preferable.
As the hydrogen bond of the HSP value (delta] H), preferably ^{6 MPa 1/2} or ^{25 MPa 1/2} or less, ^{6 MPa 1/2} or ^{13 MPa 1/2} or less is more preferable.

Examples of the organic solvent TotHSP value is ^{20 MPa 1/2} or more ^{23 MPa 1/2} or less, for example, 3-butoxy -N represented by the following structural formula (1), N-dimethyl propionamide (TotHSP value: 20. 2 MPa ^1/2 ), 3-methoxy-N, N-dimethylpropionamide represented by the following structural formula (2) (totHSP value: 22.5 MPa ^1/2 ), 3 represented by the following structural formula (3) -Ethyl-3-hydroxymethyloxetane (totHSP value: 22.6 MPa ^1/2 ), propylene glycol monopropyl ether (totHSP value: 20.1 MPa ^1/2 ), propylene glycol monomethyl ether (totHSP value: 20.4 MPa ^{1 / 2} ). These may be used individually by 1 type and may use 2 or more types together. Among these, 3-butoxy-N, N-dimethylpropionamide (totHSP value: 20.2 MPa ^1/2 ), 3-methoxy-N, N-dimethylpropionamide (totHSP value: 22.5 MPa ^1/2 ), etc. The amide solvent is preferred. By using an amide solvent such as 3-butoxy-N, N-dimethylpropionamide and 3-methoxy-N, N-dimethylpropionamide together with the urethane resin particles, the film-forming property of the urethane resin particles is promoted and higher resistance is obtained. Abrasion can be expressed. The amide solvent only needs to have an amide structure in its structure and includes the amides.

(Structural Formula (1): 3-Butoxy-N, N-dimethylpropionamide)

(Structural formula (2): N, N-dimethyl-β-methoxypropionamide)

(Structural formula (3): 3-ethyl-3-hydroxymethyloxetane)

  The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10% by mass or more and 60% by mass or less from the viewpoint of the drying property and ejection reliability of the ink, 20 mass% or more and 60 mass% or less are more preferable.

  The content of the amide solvent in the ink is preferably 0.05% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less.

<Water>
The water content in the ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass or more and 90% by mass or less, and 20% by mass from the viewpoint of ink drying property and ejection reliability. % To 60% by mass is more preferable.

  There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water; Ultrapure water etc. are mentioned. . These may be used individually by 1 type and may use 2 or more types together.

<Color material>
The color material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used alone or in combination of two or more. A mixed crystal may be used.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy pigment such as gold or silver, a metallic pigment, or the like can be used.
Carbon black produced by known methods such as contact method, furnace method, thermal method in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow as inorganic pigments Can be used.
Organic pigments include azo pigments, polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinofullerone pigments). Dye chelates (for example, basic dye type chelates, acidic dye type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used. Of these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11). And metal pigments such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).
Further, for color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, and a basic dye can be used. One kind may be used alone, or two or more kinds may be used in combination.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1,12,24,33,50,55,58,86,132,142,144,173, C.I. I. Direct Red 1,4,9,80,81,225,227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, and 35 are mentioned.

  The content of the color material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass from the viewpoints of improvement in image density, good fixability and ejection stability. It is as follows.

In order to disperse the pigment in the ink, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of dispersing the pigment surface by coating with a resin, a method of dispersing using a dispersant, Etc.
Examples of a method for introducing a hydrophilic functional group into a pigment to form a self-dispersing pigment include a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) Can be used.
As a method for coating the surface of the pigment with a resin and dispersing it, a method in which the pigment is included in microcapsules and can be dispersed in water can be used. This can be paraphrased as a resin-coated pigment. In this case, it is not necessary that all pigments blended in the ink are coated with a resin, and within a range where the effects of the present invention are not impaired, uncoated pigments and partially coated pigments are dispersed in the ink. It may be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant or high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and naphthalenesulfonic acid Na formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
An ink can be obtained by mixing a material such as water or an organic solvent with a pigment. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.
The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and other components as required, and adjusting the particle size. For dispersion, a disperser is preferably used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of maximum number because the pigment dispersion stability is good and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1% by mass. % To 50% by mass is preferable, and 0.1% to 30% by mass is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

[Mass ratio (resin particles / coloring material)]
The mass ratio (resin particles / coloring material) between the content (mass%) of the resin particles and the content (mass%) of the coloring material is from the standpoint of scratch resistance and ejection stability. 5 or more and 3.0 or less are preferable, and 0.6 or more and 3.0 or less are more preferable.

[Mass ratio (amide solvent / urethane resin particles)]
The mass ratio (amide solvent / urethane resin particles) between the content (mass%) of the amide solvent and the content (mass%) of the urethane resin particles is preferably 0.1 or more and 5.0 or less. More preferably, it is not less than .17 and not more than 4.2. When the content is 0.1 or more, the effect of forming a film is easily obtained, and when the content is 5.0 or less, the resin particles do not swell during ink storage, and the viscosity does not easily change, and storage stability. Can be improved.

[Area ratio (B / A)]
When an ink film formed with the ink of the present invention was measured by a Fourier transform infrared absorption spectrum method (hereinafter also referred to as “FTIR”), an area from a spectrum of 692 cm ⁻¹ to 707 cm ⁻¹ and a spectrum of 710 cm ^-1 740 cm ^-1 or less of the minimum point and spectral 660 cm ^-1 or more and a tangent line connecting the 690 cm ^-1 minimum point between the following area of the peak region surrounded by a between, and from the spectrum 1,731Cm ^-1 1 , the tangent line connecting the region of up to 750 cm ^-1, the minimum point between the 1,790Cm ^-1 below the minimum point and spectral 1,760Cm ^-1 or more between the spectral 1,660Cm ^-1 or more 1,690Cm ^-1 or less , The area ratio (B / A) of the area B of the peak region surrounded by. Above 1.0 or less is preferable. When the area ratio (B / A) is 0.3 or more and 1.0 or less, it is possible to achieve both the effect of improving the scratch resistance by the urethane resin particles and the effect of improving the ejection stability by the acrylic resin particles. .

For the measurement of the ink film by the Fourier transform infrared absorption spectrum method, an ATR (Attenuated Total Reflection) method of a Fourier transform infrared spectrophotometer can be used. Specifically, the surface of the ink film formed on paper (trade name: Lumi Art Gloss 130 gsm, manufactured by Stora Enso) with an ink adhesion amount of 1.12 mg / cm ² (700 mg / A4) : Using Spectrum One (manufactured by Perkin Elmer), it can be determined from the spectrum measured by the ATR method using a diamond indenter.

FIG. 3 is a schematic diagram showing the area A of the peak region and the area B of the peak region.
As shown in FIG. 3, the area A of the peak area, the spectrum 692cm and region up 707Cm ^{-1 -1,} the spectrum 710 cm ^-1 or more 740 cm ^-1 or less minimum point between and spectral 660 cm ^-1 or more 690 cm ^-1 It can be calculated using a device name: Spectrum One (manufactured by Perkin Elmer) from a peak region surrounded by a tangent line connecting the minimum points between the following. The area B of the peak area, an area from the spectrum 1,731Cm ^-1 to 1,750Cm ^-1, the minimum point and spectrum between the following spectral 1,660Cm ^-1 or more 1,690cm ^-1 1,760cm ^- It can be calculated in the same manner as the area A of the peak region from the peak region surrounded by the tangent line connecting the minimum points between ^{1 and} 1,790 cm ⁻¹ .

[Dynamic friction coefficient]
The dynamic friction coefficient of the ink film having the ink adhesion amount of 1.12 mg / cm ² (700 mg / A4) is 0.4 or less. When the dynamic friction coefficient is 0.4 or less, the slip property is improved and the image is hardly broken. Moreover, this effect can be drastically improved by combining the urethane resin particles and the wax.
The dynamic friction coefficient is such that an ink film having an ink adhesion amount of 1.12 mg / cm ² (700 mg / A4) is formed on a recording medium (paper) in an environment of a temperature of 23 ° C. and a humidity of 50% RH. The average dynamic friction coefficient from 30 mm to 50 mm from the start position when applying vertical load: 20 g / cm ² and rubbing 60 mm at a speed of 1,200 mm / min. It is defined as the dynamic friction coefficient of the surface.
The dynamic friction coefficient can be measured using HEIDON TYPE 14DR (manufactured by Shinto Kagaku Co., Ltd.) as an apparatus. As the recording medium, a trade name: Lumi Art Gloss 130 gsm (manufactured by Stora Enso) can be used.

  The dynamic friction coefficient is larger than 0.4 when the wax is not added and the acrylic resin particles or the urethane resin particles are used as a fixing resin. However, by adding the wax, the surface of the image (ink film) is improved. The dynamic friction coefficient can be 0.4 or less.

<Additives>
If necessary, a surfactant, an antifoaming agent, an antiseptic / antifungal agent, a rust inhibitor, a pH adjuster, and the like may be added to the ink.

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.
There is no restriction | limiting in particular in silicone type surfactant, According to the objective, it can select suitably. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. In addition, as the silicone surfactant, a polyether-modified silicone surfactant can be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylate. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
These may be used alone or in combination of two or more.

The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side Since both ends of the chain are modified with polydimethylsiloxane, a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant. preferable.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.
The polyether-modified silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) is represented by dimethylpolysiloxane. Examples thereof include those introduced into the side chain of Si part of siloxane.
Formula (S-1)
(In the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R ′ represents an alkyl group.)
A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Bic Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorosurfactant include perfluoroalkyl phosphate compounds, perfluoroalkylethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and in particular, fluorine-based compounds represented by the general formulas (F-1) and (F-2) A surfactant is preferred.
Formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
Formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CnF _{2n + 1} , n is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CnF _{2n + 1,} where n is 4 to 6. An integer, or CpH _{2p + 1} , p is an integer of 1-19. a is an integer of 4-14.
A commercial item may be used as said fluorosurfactant. As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250 FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova) Manufactured), Unidyne DSN-403N (produced by Daikin Industries, Ltd.) and the like. Among these, good print quality, particularly color developability, penetrability to paper, wettability, and leveling are significantly improved. FS-3100, FS-34, FS-300 manufactured by Chemours, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd. Particularly preferred are Fox PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd.

  There is no restriction | limiting in particular as content of surfactant in an ink, Although it can select suitably according to the objective, From the point which is excellent in wettability and discharge stability, and image quality improves, it is 0.001 mass. % To 5% by mass is preferable, and 0.05% to 5% by mass is more preferable.

<Antifoaming agent>
There is no restriction | limiting in particular as an antifoamer, For example, a silicone type antifoamer, a polyether type | system | group antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned. These may be used alone or in combination of two or more. Among these, a silicone type antifoaming agent is preferable from the viewpoint of excellent foam breaking effect.

<Antiseptic and fungicide>
The antiseptic / antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Rust preventive>
There is no restriction | limiting in particular as a rust preventive agent, For example, acidic sulfite, sodium thiosulfate, etc. are mentioned.

<PH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or more, and examples thereof include amines such as diethanolamine and triethanolamine.

There is no restriction | limiting in particular as a physical property of an ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.
The viscosity at 25 ° C. of the ink is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less from the viewpoint of improving the printing density and character quality and obtaining good discharge properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid amount 1.2 mL, rotation speed 50 rpm, and measurement is possible for 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12 and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Ink production method>
The ink can be produced, for example, by stirring and mixing the water, the organic solvent, the resin particles, the color material, the wax, and, if necessary, the additive. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like can be used.

<Recording medium>
The recording medium used for recording is not particularly limited, and examples thereof include plain paper, glossy paper, special paper, cloth, film, OHP sheet, and general-purpose printing paper.

<Recorded material>
The ink recorded matter of the present invention has an image formed using the ink of the present invention on a recording medium.
Recording can be performed by recording with an inkjet recording apparatus and an inkjet recording method.

Further, the recording material has, on a recording medium, an organic solvent, and an ink layer containing a coloring material, when measured by Fourier transform infrared absorption spectrum method, a region from the spectrum 692cm ^-1 to 707cm ^-1, the spectrum 710 cm ^-1 or more 740 cm ^-1 or less of the minimum point and spectral 660 cm ^-1 or more and a tangent line connecting the 690 cm ^-1 minimum point between the following area of the peak region surrounded by a between, and from the spectrum 1,731Cm ^-1 a region up to 1,750cm ^-1, tangent connecting the minimum point between the 1,790Cm ^-1 below the minimum point and spectral 1,760Cm ^-1 or more between the spectral 1,660Cm ^-1 or more 1,690Cm ^-1 or less The area ratio (B / A) of the area B of the peak region surrounded by Dynamic friction coefficient of the ink film amount is 1.12 mg / cm ² is 0.4 or less.

<Ink container>
The ink container of the present invention contains the ink of the present invention in a container, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like What has is mentioned suitably.

<Recording apparatus and recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording apparatus and the recording method are an apparatus capable of ejecting ink, various treatment liquids, and the like to a recording medium, and a method of performing recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printing surface and the back surface of the recording medium. Although it does not specifically limit as a heating means and a drying means, For example, a warm air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, what forms patterns, such as a geometric pattern, etc. includes what forms a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, for example, a continuous paper wound up in a roll shape as a recording medium. Also included are continuous paper printers.
An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective view of the apparatus. FIG. 2 is an explanatory perspective view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. A mechanism unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), yellow (Y) is packaged, for example, an aluminum laminate film It is formed by a member. The ink storage unit 411 is stored in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be discharged from the discharge heads 434 to the recording medium.

The recording apparatus can include not only a portion that ejects ink but also a device called a pre-processing device or a post-processing device.
As one mode of the pretreatment device and the posttreatment device, as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y), a pretreatment liquid and a posttreatment liquid are included. There is a mode in which a liquid container and a liquid discharge head are added, and a pretreatment liquid and a posttreatment liquid are discharged by an ink jet recording method.
As another aspect of the pretreatment apparatus and the posttreatment apparatus, there is an aspect in which, for example, a pretreatment apparatus or a posttreatment apparatus other than the ink jet recording method is provided by a blade coating method, a roll coating method, or a spray coating method.

  The method of using the ink is not limited to the ink jet recording method, and can be widely used. Besides the ink jet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

The use of the ink of the present invention is not particularly limited and can be appropriately selected depending on the purpose. Furthermore, it can be used not only to form two-dimensional characters and images using ink, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional modeled object).
A known three-dimensional modeling apparatus for modeling a three-dimensional model can be used, and is not particularly limited. For example, a three-dimensional modeling apparatus including an ink storage unit, a supply unit, a discharge unit, a drying unit, or the like is used. be able to. The three-dimensional structure includes a three-dimensional structure obtained by repeatedly applying ink. Further, a molded product obtained by processing a structure provided with ink on a substrate such as a recording medium is also included. The molded product is obtained by subjecting a recorded material or a structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, an OA device, an electric -It is suitably used for applications in which surfaces are decorated after decorating, such as meters for electronic devices, cameras, etc., and panels for operation units.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  The Martens hardness of the urethane resin particles used in the following examples and comparative examples, the area ratio (B / A) in the ink film, and the dynamic friction coefficient were measured as follows.

<Martens hardness of urethane resin particles>
The Martens hardness of the urethane resin particles is obtained by coating the urethane resin particle liquid on a slide glass (trade name: white plate glass S1111, manufactured by Matsunami Glass Industry Co., Ltd.) so as to have an average thickness of 10 μm or more, and at 60 ° C. After pre-drying for 3 hours, the resin film was obtained by drying at 100 ° C. for 6 hours. Using a micro hardness tester (device name: HM-2000, manufactured by Fischer Instruments Co., Ltd.), the Vickers indenter was pushed in with a force of 1.0 mN for 10 seconds and held for 5 seconds. It measured by pulling out in 10 second with the force of 1.0 mN.

<Area ratio (B / A)>
An ink film having an ink adhesion amount of 1.12 mg / cm ² (700 mg / A4) is formed on paper (trade name: Lumi Art Gloss 130 gsm, manufactured by Stora Enso), and the ink film is subjected to Fourier transform infrared. The determination was made from the spectrum measured by the ATR (Attenuated Total Reflection) method of the spectrophotometer. Specifically, it determined from the spectrum measured by the ATR method by the diamond indenter using apparatus name: Spectrum One (made by Perkin Elmer).

<Dynamic friction coefficient>
Apparatus: HEIDON TYPE 14DR (manufactured by Shinto Kagaku Co., Ltd.) is used, and the amount of ink adhesion is 1. An ink film of 12 mg / cm ² (700 mg / A4) is formed, the white paper is combined with the image, a vertical load of 20 g / cm ² is applied, and friction is performed by 60 mm at a speed of 1,200 mm / min. The average dynamic friction coefficient at 30 mm or more and 50 mm or less from the position was measured.

(Preparation of pigment dispersion)
<Preparation of cyan pigment dispersion>
A cyan pigment dispersion was obtained in the same manner as described in -Method A- of [Pigment surface modification treatment] in JP2012-207202A.
Specifically, C.I. I. Pigment Blue 15: 3 (trade name: Chromo Fine Blue, manufactured by Dainichi Seika Kogyo Co., Ltd.), 20 mmol of the compound of the following structural formula (5), and 200 mL of ion-exchanged water were placed in a Silverson mixer (6,000 rpm) in a room temperature environment. (0.6% by mass)) to obtain a slurry. If the pH of the resulting slurry is higher than 4, 20 mmol of nitric acid is added. After 30 minutes, sodium nitrite (20 mmol) dissolved in a small amount of ion exchange water was slowly added to the slurry. Further, the mixture was heated to 60 ° C. with stirring and reacted for 1 hour. C. above. I. A modified pigment in which a compound of the following structural formula (5) was added to the surface of Pigment Blue 15: 3 was obtained. Subsequently, the modified pigment dispersion was obtained after 30 minutes by adjusting the pH to 10 with an aqueous NaOH solution. Using the modified pigment dispersion and ion-exchanged water, ultrafiltration using a dialysis membrane is performed, and ultrasonic dispersion is further performed to have a bisphosphonic acid group as a hydrophilic functional group with a pigment concentration of 15% by mass. A cyan pigment dispersion (self-dispersing type) was obtained.
Structural formula (5)

(Preparation of pigment dispersion)
<Preparation of magenta pigment dispersion>
In preparing a cyan pigment dispersion, C.I. I. Pigment Blue 15: 3 20 g I. A magenta pigment dispersion having a pigment concentration of 15% by mass was prepared in the same manner as the cyan pigment dispersion except that the pigment red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.) was changed to 20 g. .

(Preparation of pigment dispersion)
<Preparation of yellow pigment dispersion>
In preparing a cyan pigment dispersion, C.I. I. Pigment Blue 15: 3 20 g I. A yellow pigment dispersion having a pigment concentration of 15% by mass was prepared in the same manner as in the preparation of the cyan pigment dispersion, except that Pigment Yellow 74 (trade name: First Yellow 531, manufactured by Dainichi Seika Kogyo Co., Ltd.) was changed to 20 g. Produced.

Example 1
Cyan pigment dispersion 15% by mass, 3-methoxy-N, N-dimethylpropionamide (Idemitsu Kosan Co., Ltd., totHSP value: 22.5 MPa ^1/2 ) 5% by mass, 3-ethyl-3-hydroxymethyloxetane (Ube) Kotosha Co., Ltd., totHSP value: 22.6 MPa ^1/2 ) 30% by mass, acrylic silicone resin particle liquid (trade name: Cymac US480, manufactured by Toagosei Co., Ltd.) (solid content concentration: 30 mass) %) Polycarbonate urethane resin particles 1 (Product name: Takelac W6110, manufactured by Mitsui Chemicals, Martens hardness: 10 N / mm ² ) 1 liquid (solid content concentration: 30 mass%) 4% by mass, polyethylene wax 1 (trade name: AQUACER 531, Big Chemi 1 part by weight of polyethylene wax containing 1 part by weight (solid content concentration: 30% by weight), 2 parts by weight of polyether-modified siloxane copolymer (trade name: TEGO Wet270, manufactured by Sakai Kogyo Co., Ltd.) And the remaining amount of ion-exchanged water (total 100% by mass) were mixed and stirred, and then filtered with a membrane filter having an average pore size of 0.8 μm (trade name: DISMIC-25cs, manufactured by Advantech) to obtain ink 1.

(Examples 2-18 and Comparative Examples 1-4)
In Example 1, except that the composition and content were changed to the compositions and contents shown in Tables 1 to 4, the inks 2 to 22 of Examples 2 to 18 and Comparative Examples 1 to 4 were used in the same manner as Example 1. Obtained.

In Tables 1 to 4, the trade names of the components and the names of the manufacturing companies are as follows.
<Organic solvent>
・ 3-Butoxy-N, N-dimethylpropionamide (trade name: Ecamide B100, manufactured by Idemitsu Kosan Co., Ltd., totHSP value: 20.2 MPa ^1/2 )
・ 3-Methoxy-N, N-dimethylpropionamide (trade name: Ecamide M100, manufactured by Idemitsu Kosan Co., Ltd., totHSP value: 22.5 MPa ^1/2 )
・ 3-Ethyl-3-hydroxymethyloxetane (trade name: EHO, Ube Industries, Ltd., totHSP value: 22.6 MPa ^1/2 )
Propylene glycol monomethyl ether (trade name: 1-methoxy-2-propanol, manufactured by Tokyo Chemical Industry Co., Ltd., totHSP value: 20.4 MPa ^1/2 )
Propylene glycol monopropyl ether (trade name: 1-propoxy-2-propanol, manufactured by Tokyo Chemical Industry Co., Ltd., totHSP value: 20.1 MPa ^1/2 )
1.2-propanediol (trade name: industrial propylene glycol, manufactured by ADEKA Corporation, totHSP value: 29.1 MPa ^1/2 )
1.3-propanediol (trade name: Sustena propanediol, manufactured by Dupont, totHSP value: 31.7 MPa ^1/2 )

<Resin particles>
<< Acrylic resin particles >>
Acrylic silicone resin particles: manufactured by Toa Gosei Co., Ltd., trade name: Saimak US480
Styrene acrylic resin particles: Showa Denko KK, trade name: Polysol AP-1120
<< Urethane resin particles >>
Polycarbonate urethane resin particles 1: manufactured by Mitsui Chemicals, trade name: Takelac W6110, Martens hardness: 10 N / mm ²
Polycarbonate urethane resin particles 2: manufactured by Mitsui Chemicals, trade name: Takelac WS4000, Martens hardness: 20 N / mm ²
Polycarbonate urethane resin particles 3: manufactured by Mitsui Chemicals, Inc., trade name: Takelac W6061, Martens hardness: 15 N / mm ²
Polyester urethane resin particles: manufactured by Mitsui Chemicals, Inc., trade name: Takelac WS 5984, Martens hardness: 1 N / mm ²
Polyether urethane resin particles: manufactured by Mitsui Chemicals, Inc., trade name: Takelac W5661 Martens hardness: 5 N / mm ²
The resin particles were diluted with ion-exchanged water and added so that the solid content concentration was 30% by mass.

<Wax>
-Polyethylene wax 1: manufactured by Big Chemie, trade name: AQUACER 531, melting point 130 ° C
Polyethylene wax 2: manufactured by Big Chemie, trade name: AQUACER 515, melting point 135 ° C.
Paraffin wax: manufactured by Big Chemie, trade name: AQUACER 537, melting point 110 ° C.
The wax was diluted with ion-exchanged water and added so that the solid content concentration was 30% by mass.

  Next, using the ink, “scratch resistance”, “ejection stability”, and “storage stability” were evaluated as follows. The results are shown in Table 5.

<Abrasion resistance>
Each ink was filled in an ink jet printer (device name: IPSIO GX5500, manufactured by Ricoh Co., Ltd.). Next, paper (trade name: Lumi Art Gloss 130 gsm, manufactured by Stora Enso) is set in the inkjet printer, and the ink adhesion amount is 1.12 mg / cm ² (700 mg / A4), 1,200 dpi × 1, A solid image (ink film) was recorded at a resolution of 200 dpi. After drying at 100 ° C. for 1 minute, the solid part was rubbed 20 times with a load of 400 g with the paper (trade name: Lumi Art Gloss 130 gsm, manufactured by Stora Enso) cut into 1.2 cm squares. Ink adhesion stains were measured using a device name: reflective color spectrophotometric densitometer (manufactured by X-Rite), and the density obtained by subtracting the background color of the rubbed paper was calculated. "Abrasion resistance" was evaluated. In addition, C or more is an allowable range.
-Evaluation criteria-
A: The concentration is less than 0.05 A: The concentration is 0.05 or more and less than 0.10 B: The concentration is 0.10 or more and less than 0.15 C: The concentration is 0.15 or more and less than 0.20 D: Concentration is 0.20 or more

<Discharge stability>
Each ink was filled into the ink jet printer, and the ink jet printer was allowed to stand in a decap state for 24 hours in a constant temperature bath at 40 ° C. Thereafter, the sample was taken out, head refreshing was performed from the printer driver, and “ejection stability” was evaluated based on the following evaluation criteria. In addition, C or more is an allowable range.
-Evaluation criteria-
A: Ink is ejected from all nozzles when head refreshing is less than 4 times D: Ink is ejected from all nozzles when head refreshing is 4 or more and less than 7 times C: Ink is ejected from all nozzles when head refreshing is 7 or more and less than 10 times D: All nozzles are ejected after 10 or more head refreshing

<Storage stability>
1.1 mL of each ink was sampled, put into a sample cup of a viscometer, attached to the rotary viscometer body, and allowed to stand for 1 minute, and then the rotor of the rotary viscometer was rotated, and the value after 1 minute was read. The rotational speed at the time of measuring the viscosity was adjusted so that the torque was constant within a range of 40% to 80%. The next day after ink preparation (initial viscosity) and after storage for 1 week at 23 ° C. (viscosity after storage) were measured. These viscosity values were applied to the following formula to calculate the viscosity change rate, and “storage stability” was evaluated based on the following evaluation criteria. In addition, C or more is an allowable range. The viscosity was measured at 25 ° C. using a rotational viscometer (device name: RE80L, cone plate type, manufactured by Toki Sangyo Co., Ltd.).
Viscosity change rate (%) = [(viscosity after storage−initial viscosity) / initial viscosity] × 100
-Evaluation criteria-
A: Viscosity change rate is less than 1% B: Viscosity change rate is 1% or more and less than 3% C: Viscosity change rate is 3% or more and less than 5% D: Viscosity change rate is 5% or more

As an aspect of this invention, it is as follows, for example.
<1> An ink containing an organic solvent, water, a coloring material, wax, and resin particles,
As the resin particles, including acrylic resin particles and urethane resin particles,
The mass ratio (urethane resin particles / acrylic resin particles) between the content (mass%) of the urethane resin particles and the content (mass%) of the acrylic resin particles is 0.1 or more and 0.7 or less. It is the ink characterized by this.
<2> The ink according to <1>, wherein the wax is polyethylene wax.
<3> The ink according to any one of <1> to <2>, wherein the urethane resin particles are polycarbonate urethane resin particles.
<4> The ink according to any one of <1> to <3>, wherein the urethane resin particles have a Martens hardness of 10 N / mm ² or less.
<5> The ink according to any one of <1> to <4>, wherein the acrylic resin particles are acrylic silicone resin particles.
<6> The ratio <resin particle / coloring material> between the content (mass%) of the resin particles and the content (mass%) of the coloring material is 0.5 or more and 3.0 or less. The ink according to any one of <1> to <5>.
<7> The ink according to any one of <1> to <6>, wherein a content of the wax is 0.09% by mass or more and 0.5% by mass or less in terms of solid content.
<8> Total Hansen solubility parameter of said organic solvent is an ink according the is ^{20 MPa 1/2} or more ^{23 MPa 1/2} or less to any one of <1> to <7>.
<9> The organic solvent is 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3-ethyl-3-hydroxymethyloxetane, propylene glycol monopropyl ether, and propylene The ink according to any one of <1> to <8>, wherein the ink is at least one selected from glycol monomethyl ether.
<10> The organic solvent includes an amide solvent that is at least one of 3-butoxy-N, N-dimethylpropionamide and 3-methoxy-N, N-dimethylpropionamide,
<9 wherein the mass ratio (amide solvent / urethane resin particles) of the amide solvent content (% by mass) and the urethane resin particle content (% by mass) is 0.1 to 5.0. >.
<11> The ink according to any one of <1> to <10>, wherein the resin particles have a volume average particle diameter of 10 nm to 1,000 nm.
<12> The ink according to any one of <1> to <11>, wherein the content of the acrylic resin particles is 6% by mass or more and 20% by mass or less.
<13> The ink according to any one of <1> to <12>, wherein the content of the urethane resin particles is 1% by mass or more and 4% by mass or less.
<14> The ink according to any one of <1> to <13>, wherein the content of the organic solvent is 10% by mass or more and 60% by mass or less.
<15> The ink according to any one of <1> to <14>, wherein the content of the coloring material is 1% by mass or more and 15% by mass or less.
<16> An ink containing an organic solvent, water, and a coloring material,
When the ink film formed with the ink is measured by a Fourier transform infrared absorption spectrum method,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by area of the peak area a, and the region up 1,750Cm ^-1 from the spectral 1,731cm ^-1, spectra 1,660Cm ^-1 or more 1,690Cm ^-1 minimum point between the following and spectral 1,760Cm ^-1 or The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm ^{−1 and} less is 0.3 or more and 1.0 or less,
An ink film having an ink adhesion amount of 1.12 mg / cm ² has a dynamic friction coefficient of 0.4 or less.
<17> An ink storage container, wherein the ink according to any one of <1> to <16> is stored in a container.
<18> An ink flying step of recording an image on a recording medium by applying a stimulus to the ink according to any one of <1> to <16> and causing the ink to fly. This is an ink-jet recording method.
<19> An ink jet recording apparatus comprising an ink flying unit that applies a stimulus to the ink according to any one of <1> to <16> and causes the ink to fly to record an image on a recording medium. It is.
<20> A recorded matter having a recording medium, and an ink film containing an organic solvent and a coloring material on the recording medium,
When the ink film is measured by a Fourier transform infrared absorption spectrum method,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by area of the peak area a, and the region up 1,750Cm ^-1 from the spectral 1,731cm ^-1, spectra 1,660Cm ^-1 or more 1,690Cm ^-1 minimum point between the following and spectral 1,760Cm ^-1 or The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm ^{−1 and} less is 0.3 or more and 1.0 or less,
The recorded matter is characterized in that a dynamic friction coefficient of an ink film having an ink adhesion amount of 1.12 mg / cm ² is 0.4 or less.

  <1> to <16>, the ink container according to <17>, the ink jet recording method according to <18>, the ink jet recording apparatus according to <19>, and According to the recorded matter described in <20>, the conventional problems can be solved and the object of the present invention can be achieved.

JP 2010-090266 A

400: Image forming apparatus (inkjet recording apparatus)
411: Ink container (ink container)

Claims (15)

An ink containing an organic solvent, water, a coloring material, wax, and resin particles,
As the resin particles, including acrylic resin particles and urethane resin particles,
The mass ratio (urethane resin particles / acrylic resin particles) between the content (mass%) of the urethane resin particles and the content (mass%) of the acrylic resin particles is 0.1 or more and 0.7 or less. Ink characterized by.   The ink according to claim 1, wherein the wax is polyethylene wax.   The ink according to claim 1, wherein the urethane resin particles are polycarbonate urethane resin particles. The ink according to any one of claims 1 to 3, wherein the urethane resin particles have a Martens hardness of 10 N / mm ² or less.   The ink according to claim 1, wherein the acrylic resin particles are acrylic silicone resin particles.   The mass ratio (resin particles / coloring material) of the content (% by mass) of the resin particles and the content (% by mass) of the coloring material is 0.5 or more and 3.0 or less. The ink according to any one of the above.   The ink according to any one of claims 1 to 6, wherein a content of the wax is 0.09% by mass or more and 0.5% by mass or less in terms of solid content. The total Hansen solubility parameter of the organic solvent ink according to any one of claims 1 to 7 is ^{20 MPa 1/2} or more ^{23 MPa 1/2} or less.   The organic solvent is 3-butoxy-N, N-dimethylpropionamide, 3-methoxy-N, N-dimethylpropionamide, 3-ethyl-3-hydroxymethyloxetane, propylene glycol monopropyl ether, and propylene glycol monomethyl ether The ink according to claim 1, wherein the ink is at least one selected from the group consisting of: The organic solvent includes an amide solvent which is at least one of 3-butoxy-N, N-dimethylpropionamide and 3-methoxy-N, N-dimethylpropionamide;
The mass ratio (amide solvent / urethane resin particles) of the content (mass%) of the amide solvent and the content (mass%) of the urethane resin particles is 0.1 or more and 5.0 or less. The ink described in 1. An ink containing an organic solvent, water, and a coloring material,
When the ink film formed with the ink is measured by a Fourier transform infrared absorption spectrum method,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by area of the peak area a, and the region up 1,750Cm ^-1 from the spectral 1,731cm ^-1, spectra 1,660Cm ^-1 or more 1,690Cm ^-1 minimum point between the following and spectral 1,760Cm ^-1 or The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm ^{−1 and} less is 0.3 or more and 1.0 or less,
An ink having a dynamic friction coefficient of 0.4 or less in an ink film having an ink adhesion amount of 1.12 mg / cm ² .   An ink storage container comprising the ink according to any one of claims 1 to 11 stored in a container.   An ink jet recording method comprising: an ink flying step of recording an image on a recording medium by applying a stimulus to the ink according to claim 1 and causing the ink to fly.   12. An ink jet recording apparatus comprising: ink flying means for applying a stimulus to the ink according to claim 1 and causing the ink to fly to record an image on a recording medium. A recorded matter having a recording medium, and an ink film containing an organic solvent and a color material on the recording medium,
When the ink film was measured by a Fourier transform infrared absorption spectrum method,
Surrounded from the spectrum 692cm ^-1 and the area up to 707cm ^-1, the tangent line connecting the minimum points between 690 cm ^-1 or less the minimum point and spectrum 660 cm ^-1 or more between the spectrum 710 cm ^-1 or more 740 cm ^-1 or less, by area of the peak area a, and the region up 1,750Cm ^-1 from the spectral 1,731cm ^-1, spectra 1,660Cm ^-1 or more 1,690Cm ^-1 minimum point between the following and spectral 1,760Cm ^-1 or The area ratio (B / A) of the area B of the peak region surrounded by the tangent line connecting the minimum points between 1,790 cm ^{−1 and} less is 0.3 or more and 1.0 or less,
The recorded matter, wherein an ink film having an ink adhesion amount of 1.12 mg / cm ² has a dynamic friction coefficient of 0.4 or less.