JP2019163381A - Inkjet recording ink and recording method - Google Patents

Abstract

To provide an inkjet recording ink capable of simultaneously realizing abrasion resistance, chemical resistance, and discharging properties.SOLUTION: An inkjet recording ink includes: water; a reaction initiator or a crosslinking agent, or both; and a chemical compound that reacts with the reaction initiator or the crosslinking agent, or both. The inkjet recording ink includes the reaction initiator or the crosslinking agent or both as a coated body coated with resin. The coated body has a volume average particle diameter of 50-500 nm, and the resin has a weight average molecular weight of 500-5000.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an inkjet recording ink and a recording method.

Water-based inks used in ink-jet printing do not contain volatile components in the ink and are excellent from the viewpoint of safety and environmental issues. However, bleeding is likely to occur when printing on high-quality paper or plain paper. Insufficient drying when printing on this paper, making high-speed printing difficult, and the problem that the printed ink cannot be fixed on a recording medium that does not absorb ink, such as polymer resin film, earthenware, or glass substrate Occurs.
In addition, UV ink used in inkjet printing can be printed on polymer resin films, ceramics, glass substrates, etc., and is widely compatible with substrates, and is excellent from the viewpoint of high-speed printing due to drying by UV curing. However, since it contains a lot of initiators and monomers, there are safety and environmental issues. Furthermore, the problem arises that the film thickness of the printed coating is large and the secondary workability is poor.
In order to solve such problems, various water-based ultraviolet curable inks have been disclosed.

  For example, Patent Document 1 discloses an inkjet ink containing a resin made of a compound having a radical polymerizable group, an inorganic particle dispersion, and a photo radical polymerization initiator.

  For example, Patent Literature 2 discloses a water-soluble pigment dispersant having a crosslinkable functional group, a water-soluble fixing agent having a crosslinkable functional group, and an inkjet printing ink having a crosslinker.

Ink with excellent secondary processability while maintaining the film function (film thickness and abrasion resistance) of the printed coating film similar to water-based inks, showing substrate compatibility and film function (chemical resistance) similar to UV ink not exist.
An object of the present invention is to provide an ink for ink-jet recording that can achieve both friction resistance, chemical resistance, and ejection property.

The present invention relates to the following ink for inkjet recording.
(1) An ink for inkjet recording containing water, a reaction initiator and / or a crosslinking agent, and a compound that reacts with the reaction initiator and / or the crosslinking agent, the reaction initiator or crosslinking An ink for ink jet recording, wherein the agent or both are contained as a coating coated with a resin, the volume average particle diameter of the coating is 50 nm or more and 500 nm or less, and the weight average molecular weight of the resin is 500 or more and 5000 or less.

  According to the present invention, it is possible to provide an ink for ink jet recording excellent in abrasion resistance, chemical resistance, and ejection property.

It is a figure which shows an example of the recording device using the ink of this invention. It is a perspective view of the main tank which accommodates the ink of this invention.

Although this invention concerns on said (1), following (2)-(7) is also included as embodiment.
(2) The ink for inkjet recording according to (1), wherein the compound that reacts with the reaction initiator and / or the crosslinking agent is a resin of the covering.
(3) The ink for ink jet recording contains a covering in which a crosslinking agent is coated with a resin, and the resin has a carboxyl group, a hydroxyl group, an amino group, an amide group as a polymerization reactive group that reacts with the crosslinking agent. Ink for ink-jet recording according to the above (2), having at least one selected from thiol group, epoxy group, and caprolactam group
(4) The ink for ink jet recording contains a coated body in which a reaction initiator is coated with a resin, and the resin has a (meth) acryloyl group, a vinyl group as a polymerization reactive group that reacts with the reaction initiator, The ink for inkjet recording according to (2), wherein the ink has one or more selected from a vinyl ether group and a mercapto group.
(5) The inkjet recording ink according to any one of (1) to (4), which contains two or more kinds of the reaction initiator or the crosslinking agent.
(6) The ink for inkjet recording according to any one of (1) to (5), wherein a coating film hardness of a printed matter when an image is printed is Vickers hardness of 0.1 GPa or more.
(7) The ink for inkjet recording according to any one of (1) to (6), which contains a color material.
(8) A coating in which the coated body is coated with a resin with a reaction initiator and / or a crosslinking agent and at least one selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent. The inkjet recording ink according to any one of (1) to (7), wherein the inkjet recording ink is a body.
(9) A step of forming an image by applying the inkjet recording ink according to any one of (1) to (8), and a step of causing an external stimulus to the applied inkjet recording ink to cause a curing reaction A recording method comprising:

The inkjet recording ink of the present invention is an inkjet recording ink containing water, a reaction initiator and / or a crosslinking agent, and a compound that reacts with the reaction initiator and / or the crosslinking agent, The reaction initiator or the crosslinking agent or both are contained as a coating coated with a resin, the volume average particle size of the coating is 50 nm or more and 500 nm or less, and the weight average molecular weight of the resin is 500 or more and 5000 or less. is there.
Hereafter, each component which comprises the ink for inkjet recording of this invention is demonstrated.

[Coating]
The ink of the present invention contains a coating in which one or more of a reaction initiator and / or a crosslinking agent is coated with a resin. The covering is coated with a resin having a predetermined structure and a predetermined weight average molecular weight, and is dispersed in water. This coated body has a core (inner shell) as a reaction initiator and / or a crosslinking agent, a shell as an outer shell, and the outer shell resin itself has the ability to disperse in water, or the outer shell. Although the resin itself does not have the ability to disperse in water, it is preferably a covering that can be dispersed in water by covering the covering with a dispersant. The reaction initiator and the cross-linking agent are small molecules, and the stability in water is lower than that of the polymer. For this reason, by putting an initiator and a crosslinking agent inside the shell, it does not come into contact with water, and the storage stability is improved.
In addition, by applying heat for drying after covering, the coated body softens the resin, the outer shell of the resin breaks down, the contents of the reaction initiator and / or crosslinking agent are mixed, and in response to external stimuli The crosslinking reaction is started and the film is cured. Examples of the external stimulus include drying, heat, shear stress, pH, UV, outside air, magnetism, and electricity, and heat and UV are preferable.
The content ratio of “reaction initiator and / or cross-linking agent” / “outer shell resin” in the coated body determines the ease of production of the coated body, the dispersion stability, and the ease of developing the functions of the coated body. From the viewpoint, 0.1 to 4 is preferable.

The volume average particle diameter of the covering is required to be 50 nm or more and 500 nm or less, and preferably 50 nm or more and 200 nm or less from the viewpoint of obtaining good fixability and high image hardness.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
When the volume average particle size is less than 50 nm, there are few initiators or crosslinking agents inside the coating, and the hardness of the printed coating film is lowered.
On the other hand, when the volume average particle diameter exceeds 500 nm, the gravity of the coating itself increases, and the coating is crushed and difficult to disperse.
Moreover, the calculation formula of a volume average particle diameter is as follows.

The resin that coats the reaction initiator or the crosslinking agent has a weight average molecular weight of 500 or more and 5000 or less. When the weight average molecular weight is less than 500, the ratio of the outer shell to the covering body is large, the material content of the portion that functions as the inner shell is reduced, and the function as the covering body cannot be expressed well. When the weight average molecular weight exceeds 5000, the covering is large and the dispersion stability is deteriorated.
The weight average molecular weight of the resin can be measured as, for example, an eluent: THF solution using GPC (HLC-8320GPC EcoSEC (manufactured by Tosoh Corporation)).

In the coated body, it is preferable that the reaction initiator and / or the crosslinking agent are all covered with a resin.
Whether or not the coated body is coated with a resin can be confirmed by separating the coated body, flash-freezing the coated body, then breaking the coated body, and analyzing by TEM and SEM.

The content of the covering in the total amount of the covering liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, 5 mass% or more and 50 mass% or less are more preferable.
The content of the covering in the ink is preferably 25% by mass or more and 50% by mass or less from the viewpoint of dispersion stability of the covering.

[Coating preparation method]
As a method for producing a coated body, a chemical method for preparing a coated body by forming a coated body wall using a chemical reaction, a physicochemical method for preparing a coated body wall without using a chemical reaction such as solidification or precipitation, There are three mechanical methods.

Examples of the preparation method of the chemical method include a method using an interfacial polymerization method and an in-site polymerization method.
Examples of the preparation method of the physicochemical method include a method using a submerged drying method and a coacervation method.
Examples of the method for preparing the mechanical method include a method using a spray drying method, a dry mixing method and the like.
The method for preparing the coated body is not limited to the above, and other methods may be used as long as they can contain a reaction initiator and / or a crosslinking agent and are excellent in water dispersibility.
The coating can be obtained in the form of particles in the form of water dispersion.

[Compound that reacts with reaction initiator and / or crosslinking agent]
As the compound that reacts with the reaction initiator and / or the crosslinking agent, when it is a resin of the covering, the resin does not have a polymerizable reactive group, and the reaction initiator or the crosslinking agent or Examples of the compound that reacts with both include a monomer and an oligomer, and a case where a compound that reacts with a reaction initiator and / or a crosslinking agent is included outside the ink coating. It is preferable that the resin is.

<Coating body containing reaction initiator>
[Reaction initiator]
The ink for inkjet recording of the present invention may contain a reaction initiator. Any reaction initiator may be used as long as it can generate active species such as radicals, cations, and anions by the energy of active energy rays and can initiate polymerization of a polymerizable compound (monomer or oligomer). As such a reaction initiator, known radical polymerization initiators, cationic polymerization initiators and anionic polymerization initiators can be used singly or in combination of two or more, and among them, radical polymerization initiators are used. It is preferable to do. In order to obtain a sufficient curing rate, the polymerization initiator is preferably contained in an amount of 5 to 20% by mass with respect to the total mass (100% by mass) of the ink.
Examples of radical polymerization initiators include aromatic ketones, acyl phosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, keto Examples include oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds, azo compounds, and HABI.
Examples of the cationic polymerization initiator include a photoacid generator that generates an acid when irradiated with light. A general photoacid generator is an onium salt type having a cation moiety of sulfonium ion or iodonium ion. There is also a triarylsulfonium salt type that is highly active and environmentally friendly. Specifically, CPI-100P, CPI-101A, CPI-200K, CPI-300, CPI-400 (Sanyo Kasei), WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG -367, WPAG-370, WPAG-469, WPAG-638, WPAG-699 (WAKO) B2238, B5276, B5428, C1390, D2231, D2238, D2248, D2253, D2963, F0362, I0591, M1209, M1245, M2140, M2907 , M2908, M2909, M0173, N1066, P2413, T1608, T1609, T2041, T2042, T3445, and T3446.
Examples of the anionic polymerization initiator include a photobase generator that generates a base when irradiated with light. The photobase generator includes an ionic type that generates a strong base and a nonionic type that is excellent in solubility stability. Specific examples include WPBG-266, WPBG-300, WPBG-345, WPBG-018, WPBG-140, WPBG-165, and WPBG-027.
In addition to the polymerization initiator, a polymerization accelerator (sensitizer) can be used in combination. The polymerization accelerator is not particularly limited. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid-2-ethylhexyl, N, Amine compounds such as N-dimethylbenzylamine and 4,4′-bis (diethylamino) benzophenone are preferable, and the content thereof may be appropriately set according to the polymerization initiator used and the amount thereof.

  There is no restriction | limiting in particular as content of a reaction initiator, Although it can select suitably according to the objective, From the point of coating-film sclerosis | hardenability and safety | security, 1 mass% or more and 20 mass % Or less is preferable, and 5 mass% or more and 10 mass% or less are more preferable.

[Polymerization reactive group]
When the reaction initiator is included in the ink as a coating coated with a resin, examples of the polymerization reactive group that reacts with the reaction initiator include a (meth) acryloyl group, a vinyl group, a vinyl ether group, and a mercapto group. .
As a structural feature of the compound having a polymerization reactive group, it is preferable to include any of a urethane bond, an ester bond, an amide bond, and an ether bond. For example, when the resin of the covering is a compound that reacts with a reaction initiator and has a polymerization reactive group that reacts with the reaction initiator, the resin is an aromatic urethane acrylate, an aliphatic urethane acrylate, a styrene / acrylic acid ester, It is preferable to have at least one selected from polyester acrylate, acrylic resin, and polyester resin.
Examples of the emulsion having a polymerizable reactive group include LR 9005, UA 8949, UA 9059, LR 8983, UA 9060 (BASF), UCECOAT 7571, UCECOAT 7849, UCECOAT 7773, UCECOAT 7788, UCECOAT 7177 (65). , 6828w / 45WA (VIACRYL VSC).

<Coating body in which crosslinking agent is included>
[Crosslinking agent]
Examples of the crosslinking agent include a thermosetting agent and a two-component curing agent.
The thermosetting agent refers to a material that undergoes a chemical reaction by heat, and includes a thermal radical polymerization initiator, a thermal cationic polymerization initiator, and blocked isocyanates in which the protective group is removed by heat and the reaction proceeds.
As the thermal radical polymerization initiator, A0566, A0680, A1670, A1671, A2735, A3012, B3152, B3153, C2223, D3411, D3797, D4894 (Tokyo Kasei), V-501, VA-086, VA-057, V- 50, VA-061, A-046B, and VA-044 (WAKO).
Examples of the thermal cationic polymerization initiator include B5428, C0454, C2363, and D2585 (Tokyo Kasei).
Examples of blocked isocyanates include DMP, DEM, MEKO, E-CAP (Baxenden), Corone BI-301, Corone 2507, Corone 2554 (Tosoh), Blonate IPDI-CO3HW-0516, Bronate IPDI-NH3W-0518 (Otsuchi Sangyo) ).
The two-component curing agent refers to a material in which two different types of reactive groups are mixed, or a chemical reaction proceeds by mixing and heating.
Specifically, "carbodiimide group and carboxyl group / phenolic hydroxyl group / alcohol hydroxyl group / amino group / epoxy group""isocyanate group and phenolic hydroxyl group / alcohol hydroxyl group / amino group / caprolactam group""aziridine group and carboxyl group ”“ Epoxy group and amino group / amide group ”“ Oxazoline group and carboxyl group / phenolic hydroxyl group / aromatic thiol group ”“ imide ester group and amino group ”“ NHS ester group and amino group ”“ (bis) maleimide group ” Examples include thiol group, “EDC group and carboxyl group”, “hydrazide group and aldehyde group”, and “gold and thiol group”.
There is no restriction | limiting in particular as content of a crosslinking agent, Although it can select suitably according to the objective, From the point of coating-film sclerosis | hardenability and safety, 1 mass% or more and 20 mass% with respect to coating body liquid whole quantity. The following is preferable, and 5 mass% or more and 10 mass% or less are more preferable.

[Polymerization reactive group]
When the crosslinker is coated with a resin and included in the ink, the polymerization reactive group that reacts with the crosslinker includes carboxyl groups, phenolic hydroxyl groups, alcoholic hydroxyl groups, amine groups, amide groups, aromatic thiols. And compounds having a group, an epoxy group, caprolaclam, an acid anhydride, and the like. A compound having a carboxyl group and a hydroxyl group is particularly preferred. Moreover, as a structural feature of the compound having a polymerization reactive group, it is preferable to include any of a urethane bond, an ester bond, an amide bond, and an ether bond. For example, when the resin of the coated body is a compound that reacts with the crosslinking agent and has a polymerization reactive group that reacts with the crosslinking agent, the resin includes a carboxyl group, a hydroxyl group, an amino group, an amide group, a thiol group, an epoxy group, It preferably has one or more selected from caprolactam groups.

<Coating body in which initiator and crosslinking agent are included>
[Initiator / Crosslinking agent]
Both the initiators and cross-linking agents listed above contain one or more each.

[Polymerization reactive group]
Each of the polymerization reactive group used in the initiator encapsulating type and the polymerization reactive group used in the cross-linking agent encapsulating type each contain one or more types.

The covering is a covering in which a reaction initiator and / or a crosslinking agent and at least one selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer and organic solvent are coated with a resin. There may be.
The inactive monofunctional monomer, polyfunctional monomer, oligomer, polymer, organic solvent is a monofunctional monomer, polyfunctional monomer, oligomer, polymer, which does not react with the reaction initiator and / or crosslinking agent contained in the ink, An organic solvent.
In producing the covering, the outer shell material is added after dispersing the inner shell material of the covering, and the inner shell material is coated with the outer shell material. The outer shell material is then chemically reacted to harden the outer shell. When the outer shell is hardened, if the inner shell material reacts, the reaction after printing by inkjet may not be successful. Therefore, it is preferable to use a material that does not react with the reaction initiator and / or the crosslinking agent as the inner shell material of the covering.

[monomer]
(Monofunctional monomer)
In the present invention, the monofunctional monomer means a monomer having one polymerizable ethylenically unsaturated double bond.
Examples of the monofunctional monomer having one polymerizable ethylenically unsaturated double bond used in the present invention include the following. Phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 3-methoxybutyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydixylethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropane formal monoacrylate, imide acrylate, Isoamyl Chryrate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone modified tetrahydrofurfuryl Acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, acryloylmorpholine, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinyl pyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol Monoacrylate, 2- (2-et (Xyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylation ( 4) Nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, methoxypolyethylene glycol (550) monoacrylate, and the like can be mentioned, but are not limited thereto. These monofunctional monomers may be used in combination of two or more as required.

(Polyfunctional monomer)
In the present invention, the polyfunctional monomer means a monomer having two or more polymerizable ethylenically unsaturated double bonds.
Examples of the polyfunctional monomer used in the present invention include the following. Hexadiol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol triacrylate, neopentyl glycol diacrylate, bispentaerythritol hexaacrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethoxylated 1,6-hexanediol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol Diacrylate, 2-n-butyl-2-ethyl 1,3-propane All diacrylate, hydroxypivalate neopentyl glycol diacrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane triacrylate, hydroxypivalate trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tri Propylene glycol diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, stearic acid modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, pentaerythritol tetraacrylate, caprolactone modified trimethylolpropane Triacrylate, propoxylate Lyseryl triacrylate, tetramethylol methane tetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, Neopentyl glycol oligoacrylate, 1,4-butanediol oligoacrylate, 1,6-hexanediol oligoacrylate, trimethylolpropane oligoacrylate, pentaerythritol oligoacrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl Glycol di (meth) Examples include, but are not limited to, acrylate, tripropylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and the like.
These polyfunctional monomers may be used in combination of two or more as required.

(Oligomer)
The oligomer used in the present invention has a polymerizable ethylenically unsaturated double bond, and examples thereof include aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers.
For example, the following are mentioned as goods. Nippon Chemical Synthesis Co., Ltd. UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, UV-1700B, UV-7630B, UV-6300B, UV-6640B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7630B, UV-7640B, UV-7650B, UT-5449, UT- 5454,
Sartomer CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E80, CN963E80, CN963E80, CN963E80, CN963E80, CN963E80 CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975C9797C9797C9797C9797C9797C 981A75, CN981B88, CN982, CN982A75, CN982B88, CN982E75, CN983, CN984, CN985, CN985B88, CN986, CN989, CN991, CN992, CN994, 90099C, 90099C9999 CN9009, CN9010, CN9011, CN9013, CN9018, CN9019, CN9024, CN9025, CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, N9783
Daicel-Cytec Co. EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, KRM8200, EBECRYL5129, EBECRYL8210, EBECRYL8301, EBECRYL8804, EBECRYL8807, EBECRYL9260, KRM7735, KRM8296, KRM8452, EBECRYL4858, EBECRYL8402, EBECRYL9270, EBECRYL8311, EBECRYL8701 and the like, these It can also be used in combination.
Moreover, it is also possible to use oligomers obtained by synthesis instead of commercial products, or to use these in combination.

  There is no restriction | limiting in particular as content of a monomer and an oligomer, Although it can select suitably according to the objective, 0.1 point with respect to the coating body liquid whole quantity from the point of the dispersion stability and storage stability of a coating body. The mass% is preferably 40% by mass or less and more preferably 1% by mass or more and 20% by mass or less.

[Organic solvent]
There are no particular limitations on the organic solvent, and any organic solvent can be used alone or in combination. For example, 1,2-pentanediol, 1,2-hexanediol, ethylene glycol-2-ethylhexyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Butyl ether, tripropylene glycol monomethyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, tripropylene glycol dimethyl ether, triethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol Rumonopentyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, diethylene glycol diethyl ether, triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, Examples include, but are not limited to, diethylene glycol methyl ethyl ether, triethylene glycol methyl ethyl ether, tetraethylene glycol methyl ethyl ether, tetraethylene glycol butyl methyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and propylene glycol dimethyl ether.

  The content of the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of dispersion stability and storage stability of the coating body, the content of the organic solvent is 0.1 mass relative to the total amount of the coating body liquid. % To 40% by mass is preferable, and 1% to 20% by mass is more preferable.

<Ink>
The ink of the present invention can further contain an organic solvent, water, a coloring material, a resin, an additive, and the like.
Hereinafter, the organic solvent, water, color material, resin, additive, and the like used for the ink will be described.

<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 70% by mass is more preferable.

<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 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.

<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 (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone 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.

  A color material may be contained in the ink, but the content of the color material in the case where it is included is 0.1% by mass or more and 15% by mass or less from the viewpoint of improvement in image density, good fixing property and ejection stability. Is more preferable, and more preferably 1% by mass or more and 10% by mass or less.

In order to obtain an ink by dispersing a pigment, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing, a dispersing agent is used. Method, etc.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of making it dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon) Is mentioned.
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 dispersible in water can be mentioned. 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 mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, 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.

<Resin>
The type of resin contained in the ink is not particularly limited and can be appropriately selected according to the purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene type Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
Resin particles made of these resins may be used. An ink can be obtained by mixing resin particles with a material such as a colorant or an organic solvent in a resin emulsion state in which water is dispersed as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

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 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.).

<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 the 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.
There is no restriction | limiting in particular as said polyether modified silicone surfactant, According to the objective, it can select suitably, For example, the polyalkylene oxide structure represented by a general formula (S-1) type | formula is dimethylpolyethylene. Examples thereof include those introduced into the side chain of Si part of siloxane.
(However, in the 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.

  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.

Examples of external stimuli that cause a curing reaction in the ink of the present invention include drying, heat, shear stress, pH, active energy rays such as UV, outside air, magnetism, and electricity. UV is preferable when the coating resin contains a reaction initiator, and heat is preferable when the coating resin contains a crosslinking agent.
In the case of thermosetting, 70 ° C. or higher and 200 ° C. or lower is preferable from the viewpoint of activation energy of the crosslinking agent and safety at the time of curing. In addition, since the softening point of the base material itself varies depending on the type of the base material, it is necessary to select according to the base material used. The heating time is preferably 0.5 minutes or more and 10 minutes or less from the viewpoint of the curability of the printed film and the productivity of the printed matter.

<Active energy rays>
As the active energy ray used for curing the ink of the present invention, in addition to ultraviolet rays, the polymerization reaction of polymerizable components in the composition such as electron beam, α ray, β ray, γ ray and X ray is advanced. It is not particularly limited as long as it can provide necessary energy. In particular, when a high energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. In the case of ultraviolet irradiation, mercury-free is strongly desired from the viewpoint of environmental protection, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, an ultraviolet light emitting diode (UV-LED) and an ultraviolet laser diode (UV-LD) are small, have a long lifetime, high efficiency, and low cost, and are preferable as an ultraviolet light source.

As an active energy ray, it can be hardened on conditions, such as 0.5 W / cm < ² >, integrated light quantity: 500-3000 mJ / cm < ² >, for example.

<Application>
The use of the ink of the present invention is not particularly limited as long as it is a field in which an active energy ray-curable material is generally used, and can be appropriately selected according to the purpose. Insulating materials, release agents, coating materials, sealing materials, various resists, various optical materials, and the like.

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

<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.

  The coating film hardness of the printed matter when an image is printed is preferably Vickers hardness of 0.1 GPa or more. When the Vickers hardness is 0.1 GPa or more, even if the printed film is pushed in with a pencil, it is difficult to be damaged.

<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, a drying unit used in the drying step, and an irradiation step of irradiating active energy rays in order to cure the active energy ray-curable composition. 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.
Examples of the irradiation means for irradiating the active energy rays include means using a light source such as a halogen lamp, a metahara lamp, and an LED lamp. A light source for curing the ink is irradiated with an active energy ray from the side of the head and cured to form a color image. Further, the active energy ray irradiation from the light source next to the head may be weakened or omitted, and the active energy ray may be irradiated after printing a plurality of colors. Thereby, energy saving and cost reduction can be achieved.
The recording medium is not particularly limited, and examples thereof include paper, a film, a metal, a composite material thereof, and the like, and may be in a sheet form. Moreover, even if it is the structure which enables only single-sided printing, the structure which also enables double-sided printing may be sufficient.
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.

  In the present invention, the drying temperature during recording is preferably 50 ° C. or higher in order to improve the drying property and the fixing property to the non-permeable substrate. The upper limit of the drying temperature at the time of recording is not particularly limited and can be appropriately selected according to the purpose, but is 120 ° C. or less from the viewpoint of thermal deformation of the substrate from the viewpoint of ejection reliability and thermal deformation of the substrate. preferable. Furthermore, 90 degrees C or less is more preferable from the point of the wettability with respect to the base material of an ink. The drying temperature before and after recording is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of thermal deformation of the substrate, it is 100 ° C. from the viewpoint of ejection reliability and thermal deformation of the substrate. The following is preferred.

  Further, the terms “image formation”, “recording”, “printing”, “printing”, etc. in the terms of the present invention are all synonymous.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples.

<Preparation of pigment dispersion>
<Preparation example of cyan pigment dispersion>
After premixing the following formulation mixture, it was circulated and dispersed for 7 hours in a disk-type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mm diameter zirconia ball used), and a cyan pigment with a solid content of 20% by mass A dispersion was obtained.
Pigment Blue 15: 3
(Product name: LIONOL BLUE FG-7351, manufactured by Toyo Ink Co., Ltd.) 20g
Anionic surfactant (Pionin A-51-B, Takemoto Yushi Co., Ltd.) 2g
Ion-exchanged water ... 78g

<Preparation of coated body fluid>
1. Coating Body Fluid (A) Urethane Acrylate An anchor type stirrer (stirring speed: 200 rpm) was attached to a sealed stirrer layer, and 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added and stirred. Next, Irg. After adding 16 g of 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) and stirring for 2 hours, 16 g of 4,4′-dicyclohexylmethane diisocyanate as polyisocyanate and PTMG- as polyol 1000 g (manufactured by Mitsubishi Chemical Co., Ltd., polyoxytetramethylene glycol) was added and stirred at 85 ° C. for 3 hours to prepare a covering fluid (A) so that the solid content concentration was 30% by mass.

2. Coating Body Fluid (B) Polyether Acrylate A heated reactor equipped with a closed stirrer (stirring speed: 200 rpm), an internal thermometer, a gas supply path, and a distillation head, 100 g of ion-exchanged water, 0.2 g of sodium dodecyl sulfate And stirred. Next, methyl methacrylate and Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was added and stirred for 2 hours, and then 21.7 g of ethoxylated trimethylolpropane having a hydroxyl number of 550 and acrylic acid 10 0.2 g, toluene-p-sulfonic acid 2.8 g, hydroquinone monomethyl ether 0.08 g, and 2,5-di-tert.butyl-hydroquinone 0.01 g were stirred at 90 degrees for 16 hours. Next, 0.7 g of glycidyl methacrylate was added and stirred to prepare a covering liquid (B) so that the solid content concentration was 30% by mass.

3. Coated body fluid (C) Urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared according to Irg. Other than changing to 127 (BASF, 2-Hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one) Was prepared in the same manner as the coating body fluid (A), and the coating body fluid (C) was prepared so that the solid content concentration was 30% by mass.

4). Coated body fluid (D) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared according to Irg. 184 (manufactured by BASF, 1-hydroxycyclohexyl phenyl ketone) was prepared in the same manner as in the coating body fluid (A), and a coating body fluid (D) was prepared so that the solid content concentration was 30% by mass.

5. Coated body fluid (E) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) is the same as the coating body fluid (A) except that 2FP5388 (manufactured by Hampton Research INK, 2-CARBOXY HABI) is changed. The coated body fluid (E) was prepared so that the solid content concentration was 30% by mass.

6). Coated body fluid (F) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) VA-057 (manufactured by Wako Kogyo Co., Ltd., 2,2′-azobis [N- (2-carboxyethyl) -Methyl propionamidine] n hydrate) was prepared in the same manner as the coated body fluid (A), and a coated body fluid (F) was prepared so that the solid content concentration was 30% by mass.

7). Coated body fluid (G) Urethane acrylate Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coated body fluid (A) except that 16 g of methyl methacrylate was newly added at the time of addition. The coated body fluid (G) was prepared so that the solid content concentration was 40% by mass.

8). Coated body fluid (H) urethane acrylate Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was added except that SR212 (Sartomer, 1,3-butylene glycol diacrylate) was newly added at the time of addition. Was prepared in the same manner as the coating body fluid (A), and the coating body fluid (H) was prepared so that the solid content concentration was 40% by mass.

9. Coating Body Fluid (I) Urethane Acrylate An anchor type stirrer (stirring speed: 200 rpm) was attached to a sealed stirrer layer, and 100 g of ion exchange water and 0.2 g of sodium dodecyl sulfate were added and stirred. Next, Irg. 2959 (manufactured by BASF, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one), 16 g of N-vinyl-ε-caprolactam, tri After adding 8 g of methylolpropane and stirring for 2 hours, 12 g of 4,4′-dicyclohexylmethane diisocyanate as polyisocyanate and 12 g of PTMG-1000 (manufactured by Mitsubishi Chemical Corporation, polyoxytetramethylene glycol) as a polyisocyanate were added, and the mixture was added at 85 ° C. for 3 hours. Stirring was carried out for a time, and the coating body fluid (I) was prepared so that the solid content concentration was 40% by mass.

10. Coating body fluid (J) Acrylic ester Prepare a glass container equipped with a stirrer (stirring speed: 200 rpm), a reflux condenser, and a thermometer, put 50 g of ion-exchanged water into the glass container, and sufficiently replace the air with nitrogen Then, 38 g of Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added and stirred for 2 hours.
On the other hand, 50 g of ion exchange water, Emar (Kao Corporation, sodium lauryl sulfate, anionic) 0.2 g, DKSNL-600 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether) 0.3 g, ethyl acrylate A mixed solution of 17.8 g, 8.5 g of butyl acrylate, 10.4 g of methyl methacrylate and 1.2 g of acrylic acid was prepared, and further stirred for 30 minutes with a homomixer to prepare a monomer emulsion.
The internal temperature of the glass container was raised to 80 ° C., and a monomer emulsion and a mixture of 0.1 g of ammonium persulfate (anionic) and 1 g of water were added. Then, it was made to react at 80 degreeC for 1 hour, it cooled to 30 degreeC, and the coating body liquid (J) was prepared so that solid content concentration might be 30 mass%.

11. Coated body fluid (K) polyester 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added to and stirred in a reaction vessel in which a stirrer (stirring speed: 200 rpm), a reflux condenser and a thermometer were inserted. Next, 38 g of Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added and stirred for 2 hours, and then 11.3 g of terephthalic acid, 2.0 g of isophthalic acid, 7.0 g of sebacic acid, 5.5 g of ethylene glycol, neodymium Pentyl glycol 2.2g was added and it heated at 100 degreeC for 14 hours, and the coating body liquid (K) was prepared so that solid content concentration might be 30 mass%.

12 Coating Body Fluid (L) Urethane 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added to and stirred in a reaction vessel in which a stirrer (stirring speed: 200 rpm), a reflux condenser and a thermometer were inserted. Next, 38 g of Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added and stirred for 2 hours (a).
On the other hand, polycarbonate diol (Ube Industries, ETERNACOLL UH-200) 10.0 g, polycarbonate diol (Ube Industries, ETERNACOLL UH-100) 4.3 g, neopentyl glycol (NPG) 1.6 g, 2, 2.7 g of 2-dimethylolpropionic acid (DMPA) and 16.5 g of N-methylpyrrolidone (NMP) were charged under a nitrogen stream. 19.8 g of 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI) and 0.03 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out a urethanization reaction over 5 hours. Thereafter, 0.7 g of methyl ethyl ketone oxime (MEKO) was injected, and stirring was continued for 1.5 hours at the same temperature to obtain a polyurethane prepolymer. 38 g was extracted from the mixture obtained by adding and mixing 2.1 g of triethylamine to the reaction mixture, and added to (a) under vigorous stirring.
Then, 0.8 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction, and then a coated body fluid (L) was prepared so that the solid content concentration was 30% by mass.

13 Coating body fluid (M) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was prepared in the same manner as the coating body fluid (L) except that E-03A (Nisshinbo Chemical Co., carbodiimide) was changed, A coated body fluid (M) was prepared so that the solid content concentration was 30% by mass.

14 Coating body fluid (N) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was changed to Sanfel BM-G (manufactured by Sanshin Chemical Industry Co., Ltd., bismaleimide) and coating body fluid (L) The coating body fluid (N) was prepared in the same manner so that the solid content concentration was 30% by mass.

15. Coated body fluid (O) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was prepared in the same manner as the coated body fluid (L) except that K-2020E (manufactured by Nippon Shokubai Co., Ltd., oxazoline) was used. The coated body fluid (O) was prepared so that the partial concentration was 30% by mass.

16. Coating body fluid (P) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was prepared in the same manner as the coating body fluid (L) except that 19 g of 1,2-hexanediol was newly added. The coated body fluid (P) was prepared so that the solid content concentration was 30% by mass.

17. Coated body fluid (Q) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coating liquid (A) except that 30 g of the cyan pigment dispersion was newly added. Then, the coating body fluid (Q) was prepared so that the solid content concentration was 30% by mass.

18. Coating body fluid (R) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was prepared in the same manner as the coating body fluid (L) except that 30 g of the cyan pigment dispersion was newly added. The coated body fluid (R) was prepared so that the concentration was 30% by mass.

19. Coated body fluid (S) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coating liquid (G), except that 30 g of the cyan pigment dispersion was newly added. Then, the coated body fluid (S) was prepared so that the solid content concentration was 40% by mass.

20. Coating body fluid (T) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was prepared in the same manner as the coating body fluid (P) except that 30 g of the cyan pigment dispersion was newly added. The coated body fluid (T) was prepared so that the concentration was 30% by mass.

21. Coated body fluid (U) urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coating body fluid (A) except that the solid concentration was 30% by mass. A coated body fluid (U) was prepared.

22. Coating body fluid (V) Urethane Blonate Prepared in the same manner as the coating body fluid (L) except that IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was used, so that the solid content concentration was 30% by mass ( V) was prepared.

23. Coated body fluid (W) urethane acrylate A coated body fluid (W) was prepared in the same manner as the coated body fluid (A) except that the stirring speed was changed from 200 rpm to 1000 rpm, and the solid content concentration was 30% by mass.

24. Coating Body Fluid (X) Urethane Acrylate A coating body fluid (X) was prepared in the same manner as the coating body fluid (A) except that the stirring speed was changed from 200 rpm to 50 rpm, and the solid content concentration was 30% by mass.

25. Coating body fluid (Y) Urethane acrylate Prepared in the same manner as the coating body fluid (A) except that the stirring time was changed from 2 hours to 30 minutes. did.

26. Coating body fluid (Z) Urethane acrylate Prepared in the same manner as the coating body fluid (A) except that the stirring time was changed from 2 hours to 12 hours, and the coating body fluid (Z) was prepared so that the solid content concentration was 30% by mass. did.

27. Coated body fluid (a) Urethane acrylate Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was changed to 8 g, and 14 g of Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) Irg. The coating body fluid (a) was prepared in the same manner as the coating body fluid (A) except that it was added at the same time as 1173, and the solid content concentration was 30% by mass.

28. Coating Body Fluid (b) Urethane Acrylate A coating body fluid (b) was prepared in the same manner as the coating body fluid (A) except that the stirring speed was changed from 200 rpm to 900 rpm, and the solid content concentration was 30% by mass.

29. Coating body fluid (c) Urethane acrylate A coating body fluid (c) was prepared in the same manner as the coating body fluid (A) except that the stirring speed was changed from 200 rpm to 70 rpm, and the solid content concentration was 30% by mass.

30. Coating body fluid (d) Urethane acrylate Prepared in the same manner as the coating body fluid (A) except that the stirring time was changed from 2 hours to 40 minutes, and the coating body fluid (d) was prepared so that the solid content concentration was 30% by mass. did.

31. Coated body fluid (e) Urethane acrylate Prepared in the same manner as the coated body fluid (A) except that the stirring time was changed from 2 hours to 11 hours. did.

32. Coating body fluid (f) Amine-based acrylic ester Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) When adding NK-100PM (manufactured by Nippon Shokubai Co., Polyment), coating body fluid (J) The coated body fluid (f) was prepared so that the solid content concentration was 30% by mass.

33. Coated body fluid (g) Amide acrylic ester Blonate IPDI-NH3W-0518 (Baxenden, polyisocyanate) was added except that 5 g of HEAA (KJ Chemicals, hydroxyethylacrylamide) was added. In the same manner as above, a coated body fluid (g) was prepared so that the solid content concentration was 30% by mass.

34. Coating Body Fluid (h) Thiol-based acrylate ester Blonate IPDI-NH3W-0518 (Baxenden, polyisocyanate) was added to the coating body fluid (J), except that 5 g of MTPE1 (Karenzu, pentaerythritol tetrakis) was added. The coating body fluid (h) was prepared in the same manner so that the solid content concentration was 30% by mass.

35. Coating body fluid (i) Epoxy acrylate ester Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) When adding Epolide PB3600 (manufactured by Daicel, epoxidized polybutadiene), coating body fluid (J) The coated body fluid (i) was prepared so that the solid content concentration was 30% by mass.

36. Coating body fluid (j) Caprolactone acrylic acid ester Blonate Same as coating body fluid (J) except that 5 g of CLM (manufactured by Daicel, caprolactone monomer) was added at the time of addition of IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) The coated body fluid (j) was prepared so that the solid content concentration was 30% by mass.

37. Coated body fluid (k) Aromatic urethane acrylate Prepared in the same manner as the coated body fluid (A) except that 4,4'-dicyclohexylmethane diisocyanate was changed to Coronate L (Tosoh Corporation, aromatic polyisocyanate) as the polyisocyanate. The coated body fluid (k) was prepared so that the solid content concentration was 30% by mass.

38. Coating body fluid (l) Styrene / acrylic acid ester Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added to Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one), except that 3 g of styrene monomer (Denka, styrene monomer) was added when ethyl acrylate was added Prepared in the same manner as the body fluid (J), and the coated body fluid (l) was prepared so that the solid content concentration was 30% by mass.

39. Coating body fluid (m) Polyester acrylate The same as the coating body fluid (J) except that 3 g of 701A (manufactured by Shin-Nakamura Chemical Co., Ltd., 2-hydroxy-3-acryloyloxypropyl methacrylate) was added when ethyl acrylate was added. The coated body fluid (m) was prepared so that the solid content concentration was 30% by mass.

40. Coating body fluid (n) Acrylate ester Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added to Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coating body fluid (J), and the solid content concentration was 30% by mass. A coated body fluid (n) was prepared.

41. Coating body fluid (o) Acrylic ester Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was changed to WPBG-018 (manufactured by Wako Pure Chemical Industries, Ltd.) as a photoanion generator. A coated body fluid (o) was prepared in the same manner as in A) so that the solid content concentration was 30% by mass.

42. Coated body fluid (p) Acrylic ester Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was changed to WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.) as a photocation generator. A coated body fluid (o) was prepared in the same manner as in A) so that the solid content concentration was 30% by mass.

43. Coated body fluid (q) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added to Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one), Irg. The coating body fluid (q) was prepared in the same manner as the coating body fluid (L) except that 2 g of CN09 (manufactured by Sartomer) was added as an oligomer when 1173 was added, and the solid content concentration was 30% by mass.

44. Coating body fluid (r) Urethane Blonate IPDI-NH3W-0518 (manufactured by Baxenden, polyisocyanate) was added to Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one) was prepared in the same manner as the coating body fluid (L) except that the solid content concentration was 30% by mass. A coated body fluid (r) was prepared so that

The composition of the coated body fluid (A)-(r) and the preparation method are summarized in Table 1.

(Example 1)
<Ink preparation>
Ink was prepared by mixing (stirring amount of solid content) as described below, mixing and stirring, and filtering through a 0.8 μm polypropylene filter.
Coating body fluid A (solid content concentration 30% by mass) 10.00% by mass
Solvent (3-methoxy-N, N-dimethylpropionamide (manufactured by Idemitsu Kosan Co., Ltd.),
Ecamide M-100) 10.00% by mass
Solvent (1,2-propanediol, HPD-76) 10.00% by mass
Preservative (Proxel LV (manufactured by Avicia), ALV-151) 0.05% by mass
Antifungal agent (acid sulfite, RBA-119) 0.05% by mass
Surfactant (SSA-503) 1.00% by mass
Cyan pigment dispersion 5.000 mass%
Ion exchange water

(Example 2-41, Comparative example 1-6)
Except that the ink composition in the ink preparation of Example 1 was changed to the composition shown in Table 2 below, the same ink preparation as in Example 1 was performed to obtain inks of Example 2-41 and Comparative Example 1-6. .

<Example printing>
The ink was filled in an ink jet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.), and a solid image (1200 × 1200 dpi) was printed on the PC substrate. The IPSiO GXe5500 remodeling machine enables the IPSiO GXe5500 machine to reproduce a print corresponding to a printing speed of 30 m ² / hr with a printing width of 150 cm in A4 size, and change the drying temperature before recording, during recording, and after recording. Remodeled to be able to. Further, an irradiation step was added after heat drying so that active energy rays could be irradiated as necessary.
Table 3 below shows the drying conditions of Example 1-41 and Comparative Example 1-6.

  Next, the ink was evaluated as follows. The results are shown in Table 4.

<Base material adhesion>
The solid portion of the obtained image was evaluated by counting the number of remaining cells of 100 test cells by a cross-cut peel test using a cloth adhesive tape (123LW-50 manufactured by Nichiban).
The evaluation criteria are as follows. It is desirable for practical use to have a level up to “◯”.
The evaluation results are shown in Table 5.
◎: Remaining mass number is 98 or more. ○: Remaining mass number is 90 or more and less than 98.

<Discharge reliability>
The ejection reliability was evaluated using an inkjet printer (IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.). The IPSiO GXe5500 modified machine is a modification of the IPSiO GXe5500 machine so that printing corresponding to a printing speed of 30 m ² / hr can be reproduced in A4 size with a printing width of 150 cm.
First, each of the ink jet printers was filled with ink, and after confirming that “nozzle omission” had not occurred, the ink jet printer was left for 12 hours in an environment of room temperature of 32 ° C. and humidity of 30%. After leaving for 12 hours, the nozzle check pattern was printed on a PVC film without performing cleaning maintenance, the generated “nozzle omission” was counted, and “ejection reliability” was evaluated based on the following evaluation criteria. It is desirable for practical use that the evaluation is “◯” or more. The term “nozzle missing” means that ink is not ejected and an ink image is not normally drawn.
[Evaluation criteria]
◎: No nozzle omission ○: Nozzle omission 1 or less △: Nozzle omission 2 or less ×: Nozzle omission 4 or less xx: Nozzle omission 5 or more

<Hardness>
Vickers hardness H [GPa] was measured from the load when the solid part of the obtained image was pushed using a nanoindenter (HYSITRON, manufactured by Scientaomicron) and the needle was pushed into the coating film by a depth of 100 μm. Based on the following evaluation criteria, “hardness” was evaluated.
[Evaluation criteria]
◎: 0.2 [GPa] or more ○: 0.1 [GPa] or more and less than 0.2 [GPa] Δ: 0.05 [GPa] or more and less than 0.1 [GPa] x: Less than 0.05 [GPa]

<Abrasion>
100 reciprocal images were rubbed against a solid portion of the obtained image with a friction width tester with a gold width of 3 and a load of 500 g. Based on the following evaluation criteria, “abrasion” was evaluated.
[Evaluation criteria] (Visual)
5: No change 4: Color appears on the gold band, but the image is not scratched 3: Color appears on the gold band, and the image is also scratched. No image peeling 2: The color appears in the gold band, and the image is scratched. There is less than 20% image peeling with respect to the whole. 1: The color appears in the gold width, and the image is also scratched. There is an image peeling of 20% or more and less than 50% of the whole. 0: The color appears in the gold width, and the image is scratched. There is 50% or more image peeling with respect to the whole.

<Alcohol resistance>
A 1 cm × 1 cm test piece is prepared for the solid portion of the obtained image, immersed in a 100% ethanol solution for 20 minutes, then immersed in a 75% ethanol solution for 20 minutes, and then in a 50% ethanol solution for 20 minutes. It was immersed and finally immersed in a 25% ethanol solution for 20 minutes and then rubbed with a cotton swab 5 times. Based on the following evaluation criteria, “alcohol resistance” was evaluated.
[Evaluation criteria]

<Water resistance>
A test piece of 1 cm × 1 cm was prepared on the solid portion of the obtained image, immersed in water for 24 hours, and then rubbed with a cotton swab 5 times. Based on the following evaluation criteria, “water resistance” was evaluated.
[Evaluation criteria]

<Film thickness>
For the solid part of the obtained image, perform a cross-section of the image using a guillotine cutter,
The film thickness [μm] was measured using a microscope.
[Evaluation criteria]
○: Less than 2.0 [μm] Δ: 2.0 [μm] or more and less than 5.0 [μm] ×: 5.0 [μm] or more

The solid content concentration of the pigment dispersion and the coating was measured as follows.
<Solid content>
About 1 g of the pigment dispersion or the coating liquid was weighed on an aluminum dish having a diameter of 5 cm, dried at 105 ° C. for 1 hour, and the residue was weighed.

In Example 1-22, the reaction reagent (reaction initiator or crosslinking agent) inside the coated body after being ejected from the inkjet head and the polymerization reactive group of the coated body initiate a crosslinking reaction by external stimulation, A chemical bond is formed. For this reason, it was excellent in terms of scratch resistance, hardness, water resistance, and alcohol resistance. In addition, since a large amount of solvent was contained, the film thickness was small, and the ejection reliability was high.
Since Comparative Example 1-2 did not have a crosslinked structure, the scratch resistance, hardness, and alcohol resistance were inferior.

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 each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage section 413 Ink discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube

JP 2013-199602 A JP 2012-251062 A

Claims (9)

  An ink for ink jet recording comprising water, a reaction initiator and / or a crosslinking agent, and a compound that reacts with the reaction initiator and / or the crosslinking agent, the reaction initiator or the crosslinking agent or the ink An ink for ink jet recording, wherein both are contained as a coated body coated with a resin, the volume average particle diameter of the coated body is 50 nm or more and 500 nm or less, and the weight average molecular weight of the resin is 500 or more and 5000 or less.   The ink for inkjet recording according to claim 1, wherein the compound that reacts with the reaction initiator and / or the crosslinking agent is a resin of the covering.   The ink for ink jet recording contains a covering in which a crosslinking agent is coated with a resin, and the resin has a carboxyl group, a hydroxyl group, an amino group, an amide group, a thiol group as a polymerization reactive group that reacts with the crosslinking agent. The ink for ink-jet recording according to claim 2, wherein the ink has one or more selected from an epoxy group and a caprolactam group.   The ink for ink jet recording contains a coated body in which a reaction initiator is coated with a resin, and the resin has a (meth) acryloyl group, a vinyl group, a vinyl ether group as a polymerization reactive group that reacts with the reaction initiator, The ink for inkjet recording according to claim 2, which has one or more selected from mercapto groups.   The ink for inkjet recording as described in any one of Claims 1-4 containing 2 or more types of the said reaction initiator or a crosslinking agent.   The ink for inkjet recording according to any one of claims 1 to 5, wherein a coating film hardness of the printed matter when an image is printed is Vickers hardness of 0.1 GPa or more.   The ink for inkjet recording as described in any one of Claims 1-6 containing a coloring material.   The coating is a coating in which a reaction initiator and / or a crosslinking agent and at least one selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent are coated with a resin. The ink for inkjet recording as described in any one of Claims 1-7.   A recording method comprising: a step of forming an image by applying the ink for ink jet recording according to claim 1; and a step of causing an external stimulus to cause a curing reaction to the ink for ink jet recording applied.