JP7206853B2 - Ink, printing method and inkjet printing apparatus - Google Patents

Description

The present invention relates to inks, printing methods and inkjet printing devices.

In industrial applications such as advertisements and billboards, non-permeable recording media such as plastic films are used in order to improve durability such as light resistance, water resistance, and abrasion resistance. Various inks have been developed for use in

As such inks, for example, solvent-based inks using an organic solvent as a solvent, ultraviolet curing inks containing polymerizable monomers as a main component, and the like are widely used. However, the solvent-based ink is concerned about the environmental impact due to the evaporation of the organic solvent. For the UV curable ink, the choice of polymerizable monomers to be used may be limited in terms of safety.
Therefore, water-based inks have been proposed that have less environmental impact and can be directly recorded on non-permeable recording media (see, for example, Patent Documents 1 and 2).

However, conventional water-based inks have room for improvement in fixability and adhesion to impermeable recording media.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink which is excellent in fixability and adhesion to non-permeable recording media, and which gives an image excellent in abrasion resistance and image gloss.

The above problem is solved by the following configuration 1).
1) Contains water, a surfactant, resin particles and a coloring material, the surfactant contains a polysiloxane-based surfactant with an HLB value of 10 or more, and the surfactant is a surfactant with an HLB value of less than 10 , the resin particles include styrene-acrylic resin particles, and the compound represented by the following general formula (1) is contained in an amount of 10% by mass or more and 20% by mass or less based on the total amount of the ink. Ink to be. The description of the general formula (1) is omitted here, and will be described in the following embodiments.

According to the present invention, it is possible to provide an ink which is excellent in fixability and adhesiveness to a non-permeable recording medium, and which gives an image excellent in abrasion resistance and image gloss.

FIG. 1 is a perspective explanatory view showing an example of an inkjet recording apparatus. FIG. 2 is a perspective explanatory view showing an example of a main tank in the inkjet recording apparatus.

The ink of the present invention contains water, a surfactant, resin particles and a coloring material, the surfactant contains a siloxane-based surfactant with an HLB value of 10 or more, and the surfactant has an HLB value of less than 10. It is characterized in that it does not substantially contain a surfactant, and that the resin particles contain styrene-acrylic resin particles. The ink of the present invention contains an organic solvent, an additive, etc., if necessary.
The components used in the ink are described below.

<Water>
The content of water in the ink is not particularly limited and can be appropriately selected according to the purpose. % to 60% by mass is more preferred.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and is liquid at 25° C. and 1 atm. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of water-soluble organic solvents include 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-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and other nitrogen-containing heterocyclic compounds, formamide, N-methylformamide, N,N-dimethylformamide and other amides, monoethanolamine, Examples include amines such as diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate.
It is preferable to use an alcohol with a boiling point of 240° C. or lower, and particularly preferably an alcohol with a boiling point of 180° C. or lower, because it not only functions as a wetting agent/compatibilizer but also provides good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
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. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and the like.

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

Also, the ink may contain a compound represented by the following general formula (1).

However, in the general formula (1), R ₁ , R ₂ and R ₃ each independently represent a hydrocarbon group having 1 or more and 8 or less carbon atoms.

Examples of the compound represented by the general formula (1) include 3-methoxy-N,N-dimethylpropionamide in which R ₁ , R ₂ and R ₃ are all methyl groups, and R ₁ is an n-butyl group, Examples include 3-butoxy-N,N-dimethylpropione in which R ₂ and R ₃ are methyl groups, and 3-methoxy-N,N-dimethylpropionamide is particularly preferred. A product name in which R ₁ , R ₂ and R ₃ are all methyl groups includes Equamid M100 (manufactured by Idemitsu Kosan Co., Ltd.), where R ₁ is an n-butyl group and R ₂ and R ₃ are Equamid B100 (manufactured by Idemitsu Kosan Co., Ltd.) can be mentioned as one having a methyl group.
The compound represented by the general formula (1) is used as an organic solvent. By including the compound represented by the general formula (1), it is possible to provide an ink with even better fixability, which is preferable.

The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose. 20% by mass or more and 60% by mass or less is more preferable.

The compound represented by formula (1) is preferably contained in the ink of the present invention in an amount of 5 to 20% by mass, more preferably 5 to 10% by mass.

<Color material>
The coloring 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 individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, thermal method, etc. can be used.
Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among 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 for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).
Further, for color, 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 (red red), 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.
As dyes, acid dyes, direct dyes, reactive dyes, and basic dyes can be used without particular limitation, and may be used singly or in combination of two or more.
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. and Reactive Black 3,4,35.

The content of the coloring 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 improving image density, good fixability, and ejection stability. It is below.

In order to disperse the pigment and obtain an ink, there are a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin for dispersion, and a method of dispersing using a dispersant. method, etc.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with a resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. may be
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate 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>
Inks can be obtained by mixing materials such as water and organic solvents with pigments. Ink can also be produced by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is 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 can be appropriately selected according to the purpose. % or more and 50 mass % or less is preferable, and 0.1 mass % or more and 30 mass % or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator, or the like, if necessary.

<Resin particles>
As for the type of resin particles contained in the ink of the present invention, it is necessary to contain a styrene-acrylic resin from the viewpoint that the effects of the present invention are favorably exhibited. , acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic silicone resins, and the like may be used in combination.
Ink can be obtained by mixing resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used.
The commercial products include J-450, J-734, J-7600, J-352, J-390, J-7100, J-741, J74J, J-511, J-840, J-775, HRC- 1645, HPD-71, Johnclear 7600, PDX-6102B, JDX-5050 (all manufactured by Johnson Polymer), T-YP198 (manufactured by Seiko PMC) and the like.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin particles is not particularly limited and can be appropriately selected depending on the intended purpose. From the aspect of ejection stability, it is preferably 5% by mass or more and 30% by mass or less, more preferably 5% by mass or more and 20% by mass or less.

In addition, it is preferable to use polyurethane-based resin particles together from the viewpoint of improving scratch resistance. In this embodiment, the content of the polyurethane-based resin particles is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 10% by mass or less, relative to the total amount of the ink.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. 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 ink of the invention further contains a surfactant. The surfactant includes a polysiloxane-based surfactant with an HLB value of 10 or more, and the surfactant does not substantially contain a surfactant with an HLB value of less than 10.

<Polysiloxane Surfactant>
Examples of the polysiloxane-based surfactant include compounds having a hydrophilic group or a hydrophilic polymer chain on the side chain of a compound having a polysiloxane structure (silicone-based compound) such as polydimethylsiloxane; A compound having a hydrophilic group or a hydrophilic polymer chain at the end of a compound having a polysiloxane structure (silicone-based compound) can be used. The polysiloxane-based surfactant is not limited to the above examples as long as it has a polysiloxane structure in its structure.

Examples of the hydrophilic groups and hydrophilic polymer chains include polyether groups (polyethylene oxide, polypropylene oxide, copolymers thereof, etc.), polyglycerin (C ₃ H ₆ O (CH ₂ CH(OH) CH ₂ O) _n —H, etc.), pyrrolidone, betaine (C ₃ H ₆ N ⁺ (C ₂ H ₄ ) ₂ —CH ₂ COO—, etc.), sulfate (C ₃ H ₆ O (C ₂ H ₄ O)) _n -SO ₃ Na, etc.), phosphates (C ₃ H ₆ O(C ₂ H ₄ O) _n -P(=O)OHONa, etc.), quaternary salts (C ₃ H ₆ N ⁺ (C ₂ H ₄ ) ₃ Cl ^- , etc.). However, in said chemical formula, n represents an integer of 1 or more. Among these, it is preferable to have a polyether group.
In addition, a polydimethylsiloxane having a polymerizable vinyl group at the end and other copolymerizable monomers (at least part of the monomers may be hydrophilic monomers such as (meth)acrylic acid or salts thereof. (preferable) and a vinyl copolymer having a silicone compound chain such as polydimethylsiloxane in the side chain obtained by copolymerization of the above.
Among these, a compound having a polysiloxane structure and a compound having a hydrophilic polymer chain is preferable, and it is more preferable to contain a polyether group as the hydrophilic polymer chain, and a polysiloxane surfactant is used as a hydrophobic group. A nonionic surfactant containing methylpolysiloxane and having a polyoxyethylene structure as a hydrophilic group is particularly preferred.

The HLB value of the polysiloxane surfactant is 10 or more. When the HLB value is 10 or more, excellent adhesion to various impermeable recording media can be ensured. The HLB value of the polysiloxane surfactant is preferably 10 or more and 15 or less.

Here, the HLB value means the balance between the hydrophilic group and the lipophilic group of the surfactant, and the HLB value takes values from 0 to 20. Increased hydrophilicity. The HLB value is defined by the following formula (Griffin's method).
HLB value = 20 x (sum of formula weights of hydrophilic moieties/molecular weight)

Examples of the polysiloxane-based surfactants include polyether-modified silicones and polyoxyalkylene group-containing silicone compounds as described above.

Commercially available products can be used as the polysiloxane-based surfactant. Examples of the commercially available products include KF-353 (HLB value: 10), KF-618 (HLB value: 11), KF-642 (HLB Value: 12), KF-643 (HLB value: 14), KF-6013 (HLB value: 10.0), KF-6043 (HLB value: 14.5) (Shin-Etsu Chemical Co., Ltd.), TSF4440 (HLB value : 14), TSF4452 (HLB value: 11), (Toshiba Silicon Co., Ltd.), Silface SAG002 (HLB value: 12) (manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

<Other surfactants>
As other surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, and the like may be used in combination.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions of salts in these _{fluorosurfactants} include Li, Na, K, _NH4 , _NH3CH2CH2OH , _{NH2 ( CH2CH2OH} ) ₂ , and _{NH ( CH2CH2OH} ). ₃ and the like.
Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.

However, the ink of the present invention does not substantially contain a surfactant with an HLB value of less than 10. If a surfactant with an HLB value of less than 10 is included, the effects of the present invention cannot be obtained. The term "substantially free" as used herein means that the content of surfactants having an HLB value of less than 10 in the ink is 0% by mass or more and 0.1% by mass or less.

The content of the surfactant in the ink is not particularly limited and can be appropriately selected according to the purpose. 0.001% by mass or more and 5.00% by mass or less is preferable, 0.05% by mass or more and 5.00% by mass or less, and 1.00% by mass or more and 2.00% by mass or less from the viewpoint of excellent image quality. is more preferred. In particular, it is particularly preferable that the content of the polysiloxane-based surfactant is 1.00% by mass or more and 2.00% by mass or less.

<Additive>
An antifoaming agent, an antiseptic antifungal agent, a pH adjuster, etc. may be added to the ink, if necessary.

<Antifoaming agent>
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

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

<pH adjuster>
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the ink are not particularly limited and can be appropriately selected depending on the intended purpose. For example, viscosity, surface tension, pH and the like are preferably within the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. more preferred. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., from the viewpoint that the ink is appropriately leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used.
The non-permeable substrate is a substrate having a surface with low water permeability and low absorbency, and includes materials that do not open to the outside even if there are many cavities inside. , refers to a substrate having a water absorption of 10 mL/m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the impermeable substrate, for example, plastic films such as vinyl chloride resin films, polyethylene terephthalate (PET) films, polypropylene, polyethylene and polycarbonate films can be suitably used.

The polypropylene and polyethylene are not particularly limited, for example AR1025, AR1056, AR1082, EC1082, 1082D, 1073D, 1056D, 1025D, FR1073 (Asahi DuPont Flashspun Products Co., Ltd.), P2002, P2102, P2108, P2161, P2171, P2111, P4266, P5767, P3162, P6181, P8121, P1162, P1111, P1128, P1181, P1153, P1157, P1146, P1147, P1171 (Toyobo Co., Ltd.), YPI, Aquayupo, Superyupo, Ultrayupo, Newyupo, Yupo illuminated paper , YUPO construction paper, YUPO high gloss, YUPOJET, metallic YUPO (Yupo Corporation), and the like.

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

Further, the printing method of the present invention has a step of applying ink to a material to be printed, and the ink of the present invention is used as the ink.
Further, the inkjet printing apparatus of the present invention has a liquid ejection head for ejecting ink and ink, and the ink of the present invention is used as the ink.
Examples of the printing method and the inkjet printing apparatus of the present invention are described below.

<Recording device, recording method>
The ink of the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/facsimile/copier complex machines, stereolithography machines, and the like.
In the present invention, a recording apparatus and a recording method refer to an apparatus capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the apparatus. A recording medium means a medium to which ink or various processing liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and recording method may have heating means used in the heating process and drying means used in the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, hot air heaters and infrared heaters can be used. Heating and drying can be performed before, during, or after printing.
When an infrared heater is used, at least a near-infrared irradiation device is provided.
As a near-infrared irradiation device, a device comprising a halogen lamp and a reflecting mirror is known. Products that attempt to achieve efficient heating by incorporating a halogen heater into the reflecting mirror and making it into a heating unit have been commercialized. -USD-CL300, UHUSD-CL700, UH-USD-CL1000, UH-MA1-CL300, UHMA1-CL700, UH-MA1-CL1000 (all manufactured by Ushio Inc.) and the like.
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device can be used not only as a desktop type, but also as a wide recording device that can print on A0 size recording media, and for example, can use continuous paper wound into a roll as a recording medium. A continuous feed printer is also included.

An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is housed, for example, in a container case 414 made of plastic. Thus, 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 far 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 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices.
As an aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

It should be noted that the method of using the ink is not limited to the ink jet recording method, and can be widely used. In addition to the inkjet 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 and a spray coating method can be used.

In the present invention, the terms image formation, recording, printing, and printing are all synonymous. The terms recording medium, medium, and printed material are all synonymous.

Examples and comparative examples of the present invention are shown below, but the present invention is not limited to these. In addition, "parts" in the examples are "mass parts", and "%" is "mass %" except for those in the evaluation criteria. In addition, unless otherwise specified, ink preparation and evaluation were performed under the conditions of room temperature of 25° C. and humidity of 60%. Moreover, Example 5 refers to Reference Example 5 which is not included in the present invention.

<Ink preparation>
(Preparation example of pigment dispersion)
<Preparation of black pigment dispersion>
After premixing the following formulation mixture, it was circulated and dispersed for 7 hours in a disk-type bead mill (manufactured by Shinmaru Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) to obtain a self-dispersing black pigment dispersion. (Pigment solid content concentration: 15% by mass) was obtained.
・Carbon black pigment (trade name: Monarch800, manufactured by Cabot Corporation) ... 15 parts ・Anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil Co., Ltd.) ... 2 parts ・Ion exchange Water: 83 parts

<Ink composition 1>
Ion-exchanged water was added to a total of 100 parts of the following formulation, mixed and stirred after preparation, and filtered through a 5 μm filter (Minisart manufactured by Sartorius) to obtain Ink Composition 1 of Example 1. .

Black pigment dispersion 15.00 parts J-450 (styrene acrylic resin particles, nonvolatile content 42%, manufactured by Johnson Polymer) 9.50 parts Super Flex 300 (polyurethane resin particles, nonvolatile content 30%, Taiichi Kogyo Seiyaku company) 6.70 parts KF-353 (polysiloxane surfactant, HLB value = 10, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.00 parts 1,3-butanediol 10.00 parts 3-methoxy-N,N -Dimethylpropionamide 10.00 parts 3-Methoxy-3-methylbutanol 5.00 parts Proxel LV (preservative manufactured by Avecia) 0.10 parts Ion-exchanged water remaining amount

<Ink composition 2 to 9>
Ink compositions of Examples 2 to 7 and Comparative Examples 1 and 2 were prepared in the same manner as Ink Composition 1 according to the formulation shown in Table 1. The content (parts by mass) shown in Table 1 represents the solid content concentration.

However, the following materials were used for the materials in the table that are not described above.
KF-6043 (polysiloxane surfactant, HLB value = 14.5, manufactured by Shin-Etsu Chemical Co., Ltd.)
EMALEX-SS-5602 (polysiloxane surfactant, HLB value = 9, manufactured by Nippon Emulsion Co., Ltd.)

Using the obtained ink, "adhesion", "scratch resistance", "fixability (beading)" and "image glossiness" were evaluated as follows. Table 2 shows the results.

[Formation of Solid Image]
Next, the ink is filled into an inkjet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (CPPVWP1300, manufactured by Sakurai Co., Ltd., hereinafter sometimes referred to as "PVC film") is recorded. A solid image was recorded on the medium with an ink adhesion amount of 0.6 g/cm ² . After recording, the solid image was dried on a hot plate (NINOS ND-1, manufactured by AS ONE Corporation) at 80° C. for 1 hour.
In addition, the IPSiO GXe5500 modified machine is the IPSiO GXe5500 machine, which is modified so that it can reproduce a record equivalent to a recording speed of 30 m ² /hr with a printing width of 150 cm in A4 size. It was modified so that later heating conditions (heating temperature, heating time) can be changed.

<Adhesion>
In the same manner as in the method for forming a solid image, a cross-cut peeling test was performed using a cloth adhesive tape (123LW-50, manufactured by Nichiban Co., Ltd.) on a solid image formed on a PP film recording medium (P2161, manufactured by Toyobo Co., Ltd.). , the number of remaining squares of 100 test squares was counted, and the "adhesion" to the recording medium was evaluated based on the following evaluation criteria. It is desirable for the evaluation to be B or higher for practical use.
〔Evaluation criteria〕
AA: The number of remaining squares is 98 or more A: The number of remaining squares is 90 or more and less than 98 B: The number of remaining squares is 70 or more and less than 90 C: The number of remaining squares is less than 70

<Scratch resistance>
A solid image formed on a PVC film recording medium was rubbed with a cotton cloth 10 times, and the state of pigment transfer to the cotton cloth was visually observed and evaluated according to the following criteria. It is desirable for the evaluation to be B or higher for practical use.
〔Evaluation criteria〕
A: Pigment transfer to cotton cloth is hardly observed.
B: Some pigment transfer is observed.
C: The pigment is clearly transferred.

<Fixability (Beading)>
Recording unevenness of the solid image formed on the PVC film recording medium was visually observed, and "fixability (beading)" was evaluated based on the following evaluation criteria. It is desirable for the evaluation to be B or higher for practical use.
[Evaluation criteria]
A: Very good (no beading at all)
B: Good (slight beading observed)
C: Normal (there was beading)
D: Poor (there was significant beading)

<Image Glossiness>
The 60° glossiness of the solid image formed on the PVC film recording medium was measured four times with a gloss meter (BYK Gardener, 4501), and the average gloss value was obtained. Image gloss" was evaluated. It is desirable for the evaluation to be B or higher for practical use.
〔Evaluation criteria〕
AA: Gloss value is 100 or more A: Gloss value is 90 or more and less than 100 B: Gloss value is 80 or more and less than 90 C: Gloss value is less than 80

Examples 1 and 2 are preferred embodiments of the present invention, which are excellent in adhesion and fixability, provide high image gloss even when printed on a non-permeable recording medium, and produce an image having abrasion resistance. I know you can get it.
Example 3 is an example in which the resin solid content is less than 5% by mass, resulting in inferior adhesion and abrasion resistance compared to Examples 1 and 2.
Example 4 is an example in which polyurethane resin particles are not used in combination, and results are inferior to those of Examples 1 and 2 in abrasion resistance.
Example 5 is an example in which the compound represented by the general formula (1) is not included, and results are inferior to those of Examples 1 and 2 in fixability.
Example 6 is an example in which the added amount of the surfactant is slightly small, resulting in inferior image glossiness compared to Examples 1 and 2.
Example 7 is an example in which the added amount of the surfactant is slightly large, resulting in inferior adhesion and fixability compared to Examples 1 and 2.

Comparative Example 1 is an example containing a polysiloxane-based surfactant having an HLB value of less than 10, and resulted in inferior adhesion and fixability compared to Examples.
Comparative Example 2 is an example in which the styrene-acrylic resin particles are not used, and the adhesion is inferior to that of Examples.

From the results in Table 2, it can be seen that the inks of the present invention are suitable for outdoor use. In addition, the inks of Examples 1 to 7 were excellent in adhesion, scratch resistance, fixability and image glossiness.

400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For black (K), cyan (C), magenta (M), and yellow (Y) main tank 411 ink container 413 ink outlet 414 container case 420 mechanism 434 ejection head 436 supply tube L ink container

JP 2005-220352 A JP 2011-094082 A

Claims (7)

water, a surfactant, resin particles and a coloring material, the surfactant comprises a polysiloxane-based surfactant with an HLB value of 10 or more, and the surfactant is substantially a surfactant with an HLB value of less than 10 essentially not included, the resin particles include styrene-acrylic resin particles ,
Further, an ink containing 10% by mass or more and 20% by mass or less of a compound represented by the following general formula (1) .

However, in the general formula (1), R ₁ , R ₂ and R ₃ each independently represent a hydrocarbon group having 1 or more and 8 or less carbon atoms. 2. The ink according to claim 1, containing 5% by mass or more of the resin particles based on the total amount of the ink. 3. The ink according to claim 1, wherein polyurethane resin particles are also used. The ink according to any one of claims 1 to 3 , wherein the content of the polysiloxane-based surfactant is 1.00% by mass or more and 2.00% by mass or less. 5. A printing method comprising a step of applying ink to an object to be printed, wherein the ink according to any one of claims 1 to 4 is used as the ink. 6. The printing method according to claim 5 , wherein the step of applying the ink is an inkjet printing step of ejecting ink using a liquid ejection head. An inkjet printing apparatus comprising a liquid ejection head for ejecting ink and ink, wherein the ink is the ink according to any one of claims 1 to 4 .

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