JP7054050B2 - Inkjet recording ink and recording method - Google Patents

Description

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

Water-based inks used in inkjet printing are excellent in terms of safety and environmental issues because they do not contain volatile components in the inks, but bleeding is likely to occur when printing on high-quality paper or plain paper, and printing is also possible. When printing on this paper, it is difficult to print at high speed due to insufficient drying, and the printed ink cannot be fixed on a recording medium that does not absorb ink, such as polymer resin film, pottery, and glass substrate. Occurs.
In addition, the UV ink used in inkjet printing can be printed on polymer resin films, pottery, glass substrates, etc., and is widely compatible with substrates, and is excellent from the viewpoint of high-speed printing because it dries by UV curing. However, since it contains a large amount of initiators and monomers, there are problems in terms of safety and the environment. Further, there arises a problem that the film thickness of the printed coating film is large and the secondary processability is poor.
In order to solve such a problem, various water-based ultraviolet curable inks have been conventionally disclosed.

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

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

An ink that exhibits substrate compatibility and film function (chemical resistance) comparable to UV ink, and has excellent secondary processability while maintaining the film function (thickness, abrasion resistance) of the printed coating film comparable to water-based ink. not exist.
An object of the present invention is to provide an ink jet recording ink capable of achieving both abrasion resistance, chemical resistance, and ejection resistance.

The present invention relates to the following ink jet recording inks.
(1) An ink for inkjet recording containing water, a reaction initiator, a cross-linking agent, or both, and a compound that reacts with the reaction initiator, the cross-linking agent, or both, and the reaction initiator or the cross-linking. An ink for inkjet recording in which the agent or both are contained as a coating body coated with a resin, the volume average particle size of the coating 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.

According to the present invention, it is possible to provide an inkjet recording ink having excellent scratch resistance, chemical resistance, and ejection property.

It is a figure which shows an example of the recording apparatus which uses the ink of this invention. It is a perspective view of the main tank which holds the ink of this invention.

The present invention relates to the above (1), but also includes the following (2) to (7) as embodiments.
(2) The ink jet recording ink according to (1) above, wherein the compound that reacts with the reaction initiator, the cross-linking agent, or both is the resin of the coating body.
(3) The ink for inkjet recording contains a coating body in which a cross-linking agent is coated with a resin, and the resin has a carboxyl group, a hydroxyl group, an amino group, and an amide group as polymerization reactive groups that react with the cross-linking agent. , The inkjet recording ink according to (2) above, which has one or more selected from a thiol group, an epoxy group, and a caprolactam group.
(4) The inkjet recording ink contains a coating body in which a reaction initiator is coated with a resin, and the resin has a (meth) acryloyl group, a vinyl group, etc. as polymerization reaction groups that react with the reaction initiator. The ink for inkjet recording according to (2) above, which has one or more selected from a vinyl ether group and a mercapto group.
(5) The ink jet recording ink according to any one of (1) to (4) above, which contains two or more kinds of the reaction initiator or the cross-linking agent.
(6) The inkjet recording ink according to any one of (1) to (5) above, wherein the coating film hardness of the printed matter when the 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) above, which contains a coloring material.
(8) The coating is coated with a resin on the reaction initiator, the cross-linking agent, or both, and one or more selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent. The ink for inkjet recording according to any one of (1) to (7) above, which is a body.
(9) A step of applying the inkjet recording ink according to any one of (1) to (8) above to form an image, and a step of applying an external stimulus to the applied inkjet recording ink to cause a curing reaction. Recording method having and.

The inkjet recording ink of the present invention is an inkjet recording ink containing water, a reaction initiator and / or a cross-linking agent, and a compound that reacts with the reaction initiator, the cross-linking agent, or both. When the reaction initiator, the cross-linking agent, or both are contained as a coating body coated with a resin, the volume average particle size of the coating 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. be.
Hereinafter, each component constituting the inkjet recording ink of the present invention will be described.

[Cover]
The ink of the present invention contains a coating in which one or more of the reaction initiator, the cross-linking agent, or both of them 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 coating has a reaction initiator, a cross-linking agent, or both as a core (inner shell) and a resin as a shell (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 preferable that the resin itself is a coating material that can be dispersed in water by covering the coating material with a dispersant. Reaction initiators and crosslinkers are small molecules and are less stable in water than polymers. Therefore, by putting the initiator and the cross-linking agent inside the shell, it does not come into contact with water and the storage stability is improved.
In addition, after ejection, the resin is softened by applying heat for drying, and the outer shell of the resin collapses, and the reaction initiator, cross-linking agent, or both of the contents are mixed, and in response to an external stimulus. The cross-linking reaction is initiated and the film is cured. Examples of the external stimulus include drying, heat, shear stress, pH, UV, outside air, magnetism, and electricity, but heat and UV are preferable.
The content ratio of "reaction initiator and / or cross-linking agent" / "outer shell resin" in the coating material determines the ease of preparation of the coating material, the dispersion stability, and the ease of expressing the function of the coating material. From the viewpoint, 0.1 to 4 is preferable.

The volume average particle diameter of the coating material needs to be 50 nm or more and 500 nm or less from the viewpoint of obtaining good fixability and high image hardness, and is preferably 50 nm or more and 200 nm or less.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).
When the volume average particle size is less than 50 nm, the amount of the initiator or the cross-linking agent inside the coating film is small, and the hardness of the printed coating film is low.
On the other hand, when the volume average particle size exceeds 500 nm, the gravity of the covering body itself becomes large, the covering body is crushed, and it becomes difficult to disperse.
The formula for calculating the volume average particle size is as follows.

The resin that coats the reaction initiator or the cross-linking 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 outer shell occupies a large proportion in the covering body, the material content of the portion that exerts the function of the inner shell decreases, and the function as the covering body cannot be exhibited well. When the weight average molecular weight exceeds 5000, the coating material is large and the dispersion stability is deteriorated.
The weight average molecular weight of the resin can be measured as an eluent: THF solution using, for example, GPC (HLC-8320GPC EcoSEC (manufactured by Tosoh)).

In the coated body, it is preferable that the reaction initiator, the cross-linking agent, or both of them are all coated with a resin.
It can be confirmed that the covering body is coated with the resin by separating the covering body, instantly freezing the covering body, then splitting the covering body, and analyzing by TEM and SEM.

The content of the coating material in the total amount of the coating material liquid is not particularly limited and may be appropriately selected depending on the purpose, but from the viewpoint of storage stability, 1% by mass or more and 60% by mass or less is used with respect to the total amount of the ink. It is preferable, 5% by mass or more and 50% by mass or less is more preferable.
The content of the coating material 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 material.

[Covering method]
As a method for producing a covering, a chemical method for forming a covering wall by using a chemical reaction to prepare a covering, a physicochemical method for preparing a covering wall without a chemical reaction such as coagulation or precipitation, and a method for preparing a covering. There are three mechanical methods.

Examples of the method for preparing the chemical method include a method using an interfacial polymerization method and an in-site polymerization method.
Examples of the method for preparing the physicochemical method include a method using a submerged drying method and a core selvation 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 coating is not limited to the above, and any other method may be used as long as it can contain a reaction initiator, a cross-linking agent, or both, and has excellent water dispersibility.
The coating can be obtained in the form of particles in the form of water dispersion.

[Compounds that react with reaction initiators and / or crosslinkers]
When the compound that reacts with the reaction initiator, the cross-linking agent, or both is the resin of the coating, the resin does not have a polymerizable reactive group, and the reaction initiator, the cross-linking agent, or the reaction initiator or the cross-linking agent is contained in the coating. Examples of the compound that reacts with both include a case where a monomer and an oligomer are contained, and a case where a reaction initiator, a cross-linking agent, or a compound that reacts with both of the reaction initiator and the cross-linking agent are contained in the outside of the ink coating. The resin is preferably used.

<Coating body containing reaction initiator>
[Reaction initiator]
The inkjet recording ink of the present invention may contain a reaction initiator. The reaction initiator may be any one capable of generating active species such as radicals, cations and anions by the energy of the active energy rays and initiating the polymerization of the polymerizable compound (monomer or oligomer). As such a reaction initiator, known radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators can be used alone or in combination of two or more, and among them, a radical polymerization initiator is used. It is preferable to do so. Further, 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 in order to obtain a sufficient curing rate.
Examples of the radical polymerization initiator include aromatic ketones, acylphosphine oxide compounds, aromatic onium salt compounds, organic peroxides, thio compounds (thioxanthone compounds, thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, and keto. Examples thereof include oxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, alkylamine compounds, azo compounds, HABI and the like.
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 sulfonium ion or an iodonium ion as a cation portion. There is also a triarylsulfonium salt type that is highly active and considers environmental safety. Specifically, CPI-100P, CPI-101A, CPI-200K, CPI-300, CPI-400 (SANYO CHEMICAL INDUSTRIES), WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG. -376, 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, T3446.
Examples of the anionic polymerization initiator include a photobase generator that generates a base when irradiated with light. There are two types of photobase generators: an ionic type that generates a strong base and a non-ionic type that has excellent solubility stability. Specific examples thereof include WPBG-266, WPBG-300, WPBG-345, WPBG-018, WPBG-140, WPBG-165 and WPBG-027.
Further, in addition to the above-mentioned polymerization initiator, a polymerization accelerator (sensitizer) can also be used in combination. The polymerization accelerator is not particularly limited, but 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.

The content of the reaction initiator is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of coating film curability and safety, 1% by mass or more and 20% by mass with respect to the total amount of the coating liquid. % Or less is preferable, and 5% by mass or more and 10% by mass or less is more preferable.

[Polymerization reaction group]
When the reaction initiator is contained in the ink as a coating material coated with a resin, examples of the polymerization reaction group that reacts with the reaction initiator include (meth) acryloyl group, vinyl group, vinyl ether group, mercapto group and the like. ..
As a structural feature of the compound having a polymerization reactive group, it is preferable to include any one of urethane bond, ester bond, amide bond and ether bond. For example, when the resin of the coating is a compound that reacts with the reaction initiator and has a polymerization reaction group that reacts with the reaction initiator, the resin is an aromatic urethane acrylate, an aliphatic urethane acrylate, a styrene / acrylic acid ester, or the like. It is preferable to have one or more selected from polyester acrylate, acrylic resin, and polyester resin.
Emulsions 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 7178 (Allnex), 65. , 6828w / 45WA (VIACRYL VSC) and the like.

<Coating body containing a cross-linking agent>
[Crosslinking agent]
Examples of the cross-linking agent include a thermosetting agent and a two-component curing agent.
Examples of the thermosetting agent include thermal radical polymerization initiators, thermal cationic polymerization initiators, and blocked isocyanates in which the protective group is removed by heat and the reaction proceeds.
Examples of the thermal radical polymerization initiator include 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, VA-044 (WAKO) can be mentioned.
Examples of the thermal cationic polymerization initiator include B5428, C0454, C2363 and D2685 (Tokyo Kasei).
Examples of blocked isocyanates include DMP, DEM, MEKO, E-CAP (Baxenden), Bionaz BI-301, Bionaz 2507, Bionaz 2554 (Tosoh), Blonate IPDI-CO3HW-0516, Bionaz IPDI-NH3W-0518 (Daiei Sangyo). ).
The two-component curing agent refers to a material in which a chemical reaction proceeds by mixing or mixing and heating two different types of reactive groups.
Specifically, "carbodiimide group and carboxyl group / phenol-based hydroxyl group / alcohol-based hydroxyl group / amino group / epoxy group""isocyanate group and phenol-based hydroxyl group / alcohol-based 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 thereof include a thiol group, an EDC group and a carboxyl group, a hydrazide group and an aldehyde group, and a gold and a thiol group.
The content of the cross-linking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of coating film curability and safety, 1% by mass or more and 20% by mass with respect to the total amount of the coating liquid. The following is preferable, and 5% by mass or more and 10% by mass or less is more preferable.

[Polymerization reaction group]
When the cross-linking agent is contained in the ink as a coating material coated with a resin, the polymerization reactive groups that react with the cross-linking agent include carboxyl groups, phenol-based hydroxyl groups, alcohol-based hydroxyl groups, amine groups, amide groups, and aromatic thiols. Examples thereof include a group, an epoxy group, a caprolaclam, a compound having an acid anhydride and the like. Compounds having a carboxyl group and a hydroxyl group are particularly preferable. Further, as a structural feature of the compound having a polymerization reactive group, it is preferable to include any one of a urethane bond, an ester bond, an amide bond and an ether bond. For example, when the resin of the coating is a compound that reacts with the cross-linking agent and has a polymerization reactive group that reacts with the cross-linking agent, the resin has a carboxyl group, a hydroxyl group, an amino group, an amide group, a thiol group, an epoxy group, and the like. It is preferable to have one or more selected from the caprolactam groups.

<Coating body containing initiator and cross-linking agent>
[Initiator / Crosslinker]
Both the initiator and the cross-linking agent mentioned above contain one or more of each.

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

The coating is a coating in which a reaction initiator, a cross-linking agent, or both, and one or more selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent are coated with a resin. There may be.
The inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent are monofunctional monomers, polyfunctional monomers, oligomers, polymers that do not react with the reaction initiator and / or cross-linking agent contained in the ink. Refers to an organic solvent.
When preparing the covering, the outer shell material is added after the inner shell material of the covering is dispersed, and the inner shell material is coated with the outer shell material. After that, the outer shell material is chemically reacted to harden the outer shell. When the outer shell is hardened, if the inner shell material is reacted, 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, the cross-linking agent, or both as the inner shell material of the covering body.

[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, isobolonyl 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, methoxydixyl ethyl acrylate, ethyl diglycol acrylate, cyclic trimethylolpropaneformal monoacrylate, imide acrylate, Isoamyl acrylate, ethoxylated succinic acid acrylate, trifluoroethyl acrylate, ω-carboxypolycaprolactone monoacrylate, N-vinylformamide, cyclohexyl acrylate, benzyl acrylate, methylphenoxyethyl acrylate, 4-t-butylcyclohexyl acrylate, caprolactone-modified tetrahydroflu Frill acrylate, tribromophenyl acrylate, ethoxylated tribromophenyl acrylate, 2-phenoxyethyl acrylate, acryloylmorpholin, phenoxydiethylene glycol acrylate, vinyl caprolactam, vinylpyrrolidone, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedi Methanol monoacrylate, 2- (2-ethoxyethoxy) ethyl acrylate, stearyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl acrylate, isodecyl acrylate, 3,3,5-trimethylcyclohexanol acrylate, isooctyl acrylate, octyl / decyl acrylate, Examples thereof include, but are not limited to, tridecyl acrylate, caprolactone acrylate, ethoxylated (4) nylphenol acrylate, methoxypolyethylene glycol (350) monoacrylate, and methoxypolyethylene glycol (550) monoacrylate. .. If necessary, two or more kinds of these monofunctional monomers may be used in combination.

(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-propanediol diacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane triacrylate, hydroxypivalin Trimethylolpropane triacrylate, ethoxylated phosphate triacrylate, ethoxylated tripropylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, stearic acid-modified pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylolpropanetriacrylate , Tetramethylolmethanetriacrylate, pentaerythritol tetraacrylate, caprolactone-modified trimethylolpropanetriacrylate, propoxylate glyceryltriacrylate, tetramethylolmethanetetraacrylate, pentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, 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 neopentylglycoldi (meth) acrylate, propoxylated neopentylglycoldi (meth) Examples thereof include, but are not limited to, acrylates, tripropylene glycol di (meth) acrylates, ethoxylated trimethylolpropane triacrylates, and propoxylated trimethylolpropane triacrylates.
If necessary, two or more kinds of these polyfunctional monomers may be used in combination.

(Oligomer)
Examples of the oligomer used in the present invention include polymerizable ethylenically unsaturated double bonds, such as aromatic urethane oligomers, aliphatic urethane oligomers, epoxy acrylate oligomers, polyester acrylate oligomers, and other special oligomers.
For example, the following are examples of products. UV-2000B, UV-2750B, UV-3000B, UV-3010B, UV-3200B, UV-3300B, UV-3700B, UV-6640B, UV-8630B, UV-7000B, UV-7610B, manufactured by Nippon Kagaku Synthetic Co., Ltd. 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,
CN902, CN902J75, CN929, CN940, CN944, CN944B85, CN959, CN961E75, CN961H81, CN962, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN963J85, CN966, CN966, CN966J85, CN966, CN966 CN966J75, CN968, CN969, CN970, CN970A60, CN970E60, CN971, CN971A80, CN971J75, CN972, CN973, CN973A80, CN973H85, CN973J75, CN975, CN977, CN977C70, CN978, CN798B CN982E75, CN983, CN984, CN985, CN985B88, CN986, CN989, CN991, CN992, CN994, CN996, CN997, CN999, CN9001, CN9002, CN9004, CN9005, CN9006, CN9007, CN9008, CN9009, CN9010, CN901 CN9019, CN9024, CN9025, CN9026, CN9028, CN9029, CN9030, CN9060, CN9165, CN9167, CN9178, CN9290, CN9782, CN9783, CN9788, CN9893,
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 is also possible to use them together.
It is also possible to use oligomers obtained by synthesis instead of commercial products, or to use them in combination.

The content of the monomer and the oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of dispersion stability and storage stability of the coating material, the content is 0.1 with respect to the total amount of the coating material liquid. It is preferably 1% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.

[Organic solvent]
The organic solvent is not particularly limited, and any solvent can be used alone or in combination as long as it is an organic solvent. 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 monopentyl 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, 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, propylene glycol dimethyl ether and the like, but are not limited thereto.

The content of the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of dispersion stability and storage stability of the coating material, 0.1 mass by mass with respect to the total amount of the coating material liquid. % Or more and 40% by mass or less are preferable, and 1% by mass or more and 20% by mass or less are 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, coloring material, resin, additive, etc. used for the ink will be described.

<Water>
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of ink drying property and ejection reliability, 10% by mass or more and 90% by mass or less is preferable, and 20% by mass is preferable. % 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-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, 3-methoxy-N, N- Amidos such as dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. And so on.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of the glycol ether compound 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; Examples thereof 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 the permeability of ink when paper is used as a recording medium.

The content of the organic solvent 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 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, 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 color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, 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, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI 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 Calcium 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As the dye, for example, 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. Hood 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. Dylekdo 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, 35 can be mentioned.

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

In order to disperse the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing 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) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effect of the present invention is 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 represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and Naphthalene sulfonic acid Na formalin condensate can also be suitably used as a dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary to adjust the particle size. It is good to use a disperser for dispersion.
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 the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac 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, good ejection stability can be obtained and the image density is increased by 0.1 mass. % Or more and 50% by mass or less are preferable, and 0.1% by mass or more and 30% by mass or less are more preferable.
It is preferable that the pigment dispersion is degassed by filtering coarse particles with a filter, a centrifuge, or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, etc. 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. It is possible to obtain ink by mixing resin particles with a material such as a coloring material or an organic solvent in the state of a resin emulsion in which water is used as a dispersion medium. As the resin particles, those synthesized as appropriate may be used, or commercially available products may be used. Further, these may be used alone or in combination of two or more kinds of resin particles.

The volume average particle size of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good fixability and high image hardness, 10 nm or more and 1,000 nm or less are preferable. More than 200 nm is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle size can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac 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, but from the viewpoint of improving image quality such as ejection stability and image density, the maximum frequency in terms of the maximum number of inks. Is preferably 20 nm or more and 1000 nm or less, and 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 Microtrac Bell Co., Ltd.).

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

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.
Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, side chain double-ended modified polydimethylsiloxane, and the like. Those having an oxyethylene group and a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain includes 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. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルション株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain-modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side. Examples thereof include polydimethylsiloxane modified at both ends of the chain, and a polyether-modified silicone-based surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant, and is particularly effective. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) may be dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Nippon 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 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<Defoamer>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

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

<Rust inhibitor>
The rust preventive is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjusting agent 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.

The physical characteristics of the ink are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25 ° C. 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 print density and character quality and obtaining good ejection properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. As the measurement conditions, it is possible to measure at 25 ° C. with a standard cone rotor (1 ° 34'× R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 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 preferably 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 that comes into contact with the liquid.

Examples of the external stimulus that causes the ink of the present invention to undergo a curing reaction include drying, heat, shear stress, active energy rays such as pH and UV, outside air, magnetism, and electricity. When the coating resin contains a reaction initiator, UV is preferable, and when the coating resin contains a cross-linking agent, heat is preferable.
In the case of thermosetting, it is preferably 70 ° C. or higher and 200 ° C. or lower from the viewpoint of activation energy of the cross-linking agent and safety at the time of curing. Since the softening point of the base material itself differs depending on the type of the base material, it is necessary to select it 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 ray>
As the active energy rays used for curing the ink of the present invention, in addition to ultraviolet rays, in addition to ultraviolet rays, in order to promote the polymerization reaction of polymerizable components in the composition such as electron rays, α rays, β rays, γ rays and X-rays. It is not particularly limited as long as it can provide the necessary energy. In particular, when a high-energy light source is used, the polymerization reaction can proceed without using a polymerization initiator. Further, 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. Further, the ultraviolet light emitting diode (UV-LED) and the ultraviolet laser diode (UV-LD) are compact, have a long life, have high efficiency, and are low in cost, and are preferable as an ultraviolet light source.

As the active energy ray, it can be cured under the conditions of, for example, 0.5 W / cm ² and the integrated light amount: 500-3000 mJ / cm ² .

<Use>
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 depending on the intended purpose. For example, a molding resin, a paint, or an adhesive. , Insulating material, mold release agent, coating material, sealing material, 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, or the like can be used, but good image formation is possible even if a non-permeable base material is used.
The non-permeable base material is a base material having a surface having a low water permeability and absorbability, and includes a material that does not open to the outside even if there are many cavities inside, and more quantitatively. , 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, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, polypropylene, polyethylene, or a polycarbonate film can be preferably used.

<Recorded material>
The ink recording material of the present invention comprises an image formed by using the ink of the present invention on a recording medium.
It can be recorded by an inkjet recording device and an inkjet recording method to obtain a recorded material.

The hardness of the coating film of the printed matter when the image is printed is preferably Vickers hardness of 0.1 GPa or more. If the Vickers hardness is 0.1 GPa or more, even if the printing film is pushed in with a pencil, it is not easily scratched.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method for recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, a pretreatment device, a device called a posttreatment device, and the like. ..
The recording apparatus and recording method may include a heating means used in the heating step, a drying means used in the drying step, and an irradiation step of irradiating the active energy ray-curable composition in order to cure the active energy ray-curable composition. The heating means and the drying means include, for example, means for heating and drying the printed surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot 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 metal halide lamp, and an LED lamp. The light source for curing the ink irradiates an active energy ray from the side of the head to cure the ink, and forms a color image. Further, the activation of the active energy ray from the light source beside the head may be weakened or omitted, and the active energy ray may be irradiated after printing a plurality of colors. This makes it possible to save energy and reduce costs.
The recording medium is not particularly limited, and examples thereof include paper, film, metal, and composite materials thereof, and may be in the form of a sheet. Further, the configuration may be such that only single-sided printing is possible or double-sided printing is possible.
Further, the recording device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form three-dimensional images are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous book printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism portion 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, a package of an aluminum laminated film or the like. It is formed of members. The ink container 411 is housed 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 behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

In the present invention, the drying temperature at the time of recording is preferably 50 ° C. or higher in order to improve the drying property and the fixing property to the impermeable substrate. The upper limit of the drying temperature at the time of recording is not particularly limited and can be appropriately selected depending on the purpose, but 120 ° C. or less is set from the viewpoint of discharge reliability and thermal deformation of the base material. preferable. Further, 90 ° C. or lower is more preferable from the viewpoint of wettability of the ink to the substrate. The drying temperature before and after recording is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of discharge reliability and thermal deformation of the base material, 100 ° C. The following is preferable.

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

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

<Preparation of coating fluid>
1. 1. Coating fluid (A) Urethane
An anchor type stirrer (stirring speed: 200 rpm) was attached to the closed stir 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 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF) and stirring for 2 hours, 16 g of 4,4'-dicyclohexylmethane diisocyanate as polyisocyanate and PTMG- as a polyol. 16 g of 1000 (polyoxytetramethylene glycol manufactured by Mitsubishi Chemical Corporation) was added and stirred at 85 ° C. for 3 hours to prepare a coating liquid (A) so that the solid content concentration was 30% by mass.

2. 2. Coating liquid (B) Polyether acrylate A heating reactor equipped with a closed stirrer (stirring speed: 200 rpm), internal thermometer, gas supply path, and distillation head, ion-exchanged water 100 g, sodium dodecyl sulfate 0.2 g. Was added and stirred. Then methyl methacrylate and Irg. After adding 16 g of each of 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF) and stirring for 2 hours, 21.7 g of ethoxylated trimetylolpropane having a hydroxyl value of 550 and acrylic acid 10 .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 ° C. for 16 hours. Next, 0.7 g of glycidyl methacrylate was added and stirred to prepare a coating body fluid (B) so that the solid content concentration was 30% by mass.

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

4. Cover fluid (D) urethane
Irg. 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one) was added to Irg. The coating body fluid (D) was prepared in the same manner as the coating body fluid (A) except that it was changed to 184 (1-hydroxycyclohexylphenylketone manufactured by BASF) so that the solid content concentration was 30% by mass.

5. Coating body fluid (E) Urethane
Irg. Same as the body fluid (A) except that 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one) was changed to 2FP5388 (Hampford Research INK, 2-CARBOXY HABI). The coating body fluid (E) was prepared so that the solid content concentration was 30% by mass.

6. Cover fluid (F) urethane
Irg. 1173 (BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one) to VA-057 (Wako Kogyo Co., Ltd., 2,2'-azobis [N- (2-carboxyethyl)) It was prepared in the same manner as the coating liquid (A) except that it was changed to -2-methylpropion amidine] n hydrate), and the coating liquid (F) was prepared so that the solid content concentration was 30% by mass.

7. Cover fluid (G) urethane
Irg. Prepared in the same manner as the coating body fluid (A) except that 16 g of methyl methacrylate was newly added at the time of addition of 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF). The coating body fluid (G) was prepared so that the solid content concentration was 40% by mass.

8. Cover fluid (H) urethane
Irg. Except for the addition of 16 g of SR212 (1,3-butylene glycol diacrylate, manufactured by Sartmer) when 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one, manufactured by BASF) was newly added. 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 fluid (I) Urethane
An anchor type stirrer (stirring speed: 200 rpm) was attached to the closed stir layer, and 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added and stirred. Next, Irg. 2959 (BASF, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one) 16 g, N-vinyl-ε-caprolactum 16 g, trimethylolpropane After adding 8 g of trimethylolpropane and stirring for 2 hours, 12 g of 4,4'-dicyclohexylmethanediisocyanate as a polyisocyanate and 12 g of PTMG-1000 (polyoxytetramethylene glycol manufactured by Mitsubishi Chemical Corporation) as a polyol are added and 3 at 85 ° C. After stirring for hours, the coating liquid (I) was prepared so that the solid content concentration was 40% by mass.

10. Prepare a glass container equipped with a coating liquid (J) acrylic acid ester stirrer (stirring speed: 200 rpm), a reflux condenser, and a thermometer, put 50 g of ion-exchanged water in the glass container, and sufficiently replace the air with nitrogen. After that, 38 g of Blonate IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added and the mixture was stirred for 2 hours.
On the other hand, ion-exchanged water 50 g, Emar (manufactured by Kao Co., Ltd., sodium lauryl sulfate, anionic type) 0.2 g, DKSNL-600 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether) 0.3 g, ethyl acrylate A mixed solution of 17.8 g, butyl acrylate 8.5 g, methyl methacrylate 10.4 g and acrylic acid 1.2 g was prepared, and further stirred with a homomixer for 30 minutes 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, respectively. Then, the reaction was carried out at 80 ° C. for 1 hour, and the mixture was cooled to 30 ° C. to prepare a coating liquid (J) so that the solid content concentration was 30% by mass.

11. 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added to a reaction vessel into which a coated liquid (K) polyester stirrer (stirring speed: 200 rpm), a reflux condenser and a thermometer were inserted, and the mixture was stirred. Next, 38 g of Blone IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added and stirred for 2 hours, after which 11.3 g of terephthalic acid, 2.0 g of isophthalic acid, 7.0 g of sebacic acid, 5.5 g of ethylene glycol and neo. 2.2 g of pentyl glycol was added and heated at 100 ° C. for 14 hours to prepare a coating liquid (K) so that the solid content concentration was 30% by mass.

12. 100 g of ion-exchanged water and 0.2 g of sodium dodecyl sulfate were added to a reaction vessel into which a coated liquid (L) urethane stirrer (stirring speed: 200 rpm), a reflux condenser and a thermometer were inserted, and the mixture was stirred. Next, 38 g of Bronate IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added and stirred for 2 hours (a).
On the other hand, in another reaction vessel, 10.0 g of polycarbonate diol (ETERNACOLL UH-200 manufactured by Ube Kosan), 4.3 g of polycarbonate diol (ETERNACOLL UH-100 manufactured by Ube Kosan), 1.6 g of neopentyl glycol (NPG), 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 dilaurylate (catalyst) were added and heated to 90 ° C., and a urethanization reaction was carried out over 5 hours. Then, 0.7 g of methylethylketone oxime (MEKO) was injected, and stirring was continued at the same temperature for 1.5 hours to obtain a polyurethane prepolymer. From the reaction mixture to which 2.1 g of triethylamine was added and mixed, 38 g was extracted and added to (a) under strong 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 coating 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 (Polyisocyanate manufactured by Baxenden) was prepared in the same manner as the coating body fluid (L) except that it was changed to E-03A (Carbodiimide manufactured by Nisshinbo Chemical Co., Ltd.). The coating 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 (Polyisocyanate manufactured by Baxenden) is replaced with Sanfel BM-G (Bismaleimide manufactured by Sanshin Chemical Industry Co., Ltd.). The coating liquid (N) was prepared in the same manner so that the solid content concentration was 30% by mass.

15. Coating body fluid (O) Urethane Blonate IPDI-NH3W-0518 (Polyisocyanate manufactured by Baxenden) was prepared in the same manner as the coating body fluid (L) except that it was changed to K-2020E (Oxazoline manufactured by Nippon Shokubai), and solid. The coating body fluid (O) was prepared so that the component concentration was 30% by mass.

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

17. Cover fluid (Q) urethane
Irg. Prepared in the same manner as the coating body fluid (A) except that 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF) was newly added at the time of addition of 30 g of a cyan pigment dispersion. 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 (polyisocyanate manufactured by Baxenden) was prepared in the same manner as the coating body fluid (L) except that 30 g of a cyan pigment dispersion was newly added at the time of addition. The coating body fluid (R) was prepared so that the concentration was 30% by mass.

19. Cover fluid (S) urethane
Irg. Prepared in the same manner as the coating body fluid (G) except that 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF) was newly added at the time of addition of 30 g of a cyan pigment dispersion. Then, the coating 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 (polyisocyanate manufactured by Baxenden) was prepared in the same manner as the coating body fluid (P) except that 30 g of a cyan pigment dispersion was newly added at the time of addition. The coating body fluid (T) was prepared so that the concentration was 30% by mass.

21. Cover fluid (U) urethane
Irg. Prepared in the same manner as the body fluid (A) except that 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one, manufactured by BASF) was removed, and the solid content concentration was 30% by mass. Propane fluid (U) was prepared.

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

23. Cover fluid (W) urethane
The coating body fluid (W) was prepared in the same manner as the coating 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. Cover fluid (X) urethane
The 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. Cover fluid (Y) urethane
The coating body fluid (Y) was prepared in the same manner as the coating body fluid (A) except that the stirring time was changed from 2 hours to 30 minutes, and the solid content concentration was 30% by mass.

26. Cover fluid (Z) urethane
The coating body fluid (Z) was 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 solid content concentration was 30% by mass.

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

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

31. Coating body fluid (e) Urethane
The coating was prepared in the same manner as the coating liquid (A) except that the stirring time was changed from 2 hours to 11 hours, and the coating liquid (e) was prepared so that the solid content concentration was 30% by mass.

32. Coating body fluid (f) Amine-based acrylic acid ester Blonate IPDI-NH3W-0518 (Polyisocyanate manufactured by Baxenden) was added, except that 5 g of NK-100PM (Polymento manufactured by Nippon Shokubai Co., Ltd.) was added. The coating body fluid (f) was prepared so that the solid content concentration was 30% by mass.

33. Coating body fluid (g) Amide-based acrylic acid ester Blonate IPDI-NH3W-0518 (Polyisocyanate manufactured by Baxenden) was added at the time of addition, except that 5 g of HEAA (Hydroxyethyl acrylamide manufactured by KJ Chemicals) was added. The coating body fluid (g) was prepared so that the solid content concentration was 30% by mass.

34. Coating body fluid (h) Thiol-based acrylic acid ester Blonate IPDI-NH3W-0518 (Polyisocyanate manufactured by Baxenden) was added with MTPE1 (Pentaerythritol Tetrakis manufactured by Karens) except that 5 g was added. The coating liquid (h) was prepared in the same manner so that the solid content concentration was 30% by mass.

35. Coating body fluid (i) Epoxy-based acrylic acid ester Blonate IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added at the time of addition, except that 5 g of Epolide PB3600 (epoxidized polybutadiene manufactured by Daicel) was added. The coating body fluid (i) was prepared so that the solid content concentration was 30% by mass.

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

37. Coating body fluid (k) Prepared in the same manner as the coating body fluid (A) except that 4,4'-dicyclohexylmethane diisocyanate was changed to coronate L (Aromatic polyisocyanate manufactured by Tosoh Corporation) as an aromatic urethane polyisocyanate. , The coating 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 (polyisocyanate manufactured by Baxenden) was added to Irg. Covered to 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one manufactured by BASF) except that 3 g of styrene monomer (styrene monomer manufactured by Denka) was added when ethyl acrylate was added. It was 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 Same as coating body fluid (J) except that 3 g of 701A (2-hydroxy-3-acryloyloxypropyl methacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) was added when ethyl acrylate was added. The coating body fluid (m) was prepared so that the solid content concentration was 30% by mass.

40. Coating body fluid (n) Acrylic acid ester Bronate IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added to Irg. Prepared in the same manner as the body fluid (J) except that it was changed to 1173 (2-hydroxy-2-methyl-1-phenyl-propane-1-one, manufactured by BASF), and the solid content concentration is 30% by mass. A body fluid (n) was prepared.

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

42. Coating body fluid (p) Acrylic acid ester Irg. Cover body fluid (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one) except that it was changed to WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.) as a photocation generator. The coating liquid (o) was prepared in the same manner as in A) so that the solid content concentration was 30% by mass.

43. Coating body fluid (q) Urethane Blonate IPDI-NH3W-0518 (polyisocyanate manufactured by Baxenden) was added to Irg. It was changed to 1173 (manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propane-1-one), and Irg. The coating was prepared in the same manner as the coating liquid (L) except that 2 g of CN09 (manufactured by Sartmer) was added as an oligomer at the time of addition of 1173, and the coating liquid (q) was prepared so that the solid content concentration was 30% by mass.

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

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

(Example 1)
<Ink preparation>
The ink was prepared by mixing and stirring as described below (in terms of solid content) and filtering with a 0.8 μm polypropylene filter.
Cover fluid A (solid content concentration 30% by mass) 10.00% by mass
Solvent (3-methoxy-N, N-dimethylpropionamide (manufactured by Idemitsu Kosan Co., Ltd.),
Equamid M-100) 10.00% by mass
Solvent (1,2-propanediol, HPD-76) 10.00% by mass
Preservative (Proxel LV (manufactured by Avisia Co., Ltd.), 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 liquid 5.000% by mass
Ion-exchanged water remaining amount

(Example 2-41, Comparative Example 1-6)
In the same manner as in the ink preparation of Example 1 except that the ink composition in the ink preparation of Example 1 was changed to the composition shown in Table 2 below, the inks of Example 2-41 and Comparative Example 1-6 were obtained. ..

<Printing for examples>
The ink was filled in an inkjet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.), and a solid image (1200 × 1200 dpi) was printed on a PC substrate. The IPSiO GXe5500 modified machine enables the IPSiO GXe5500 machine to reproduce printing equivalent to a printing speed of 30 m ² / hr with a printing width of 150 cm in A4 size, and changes the drying temperature before, during, and after recording. I remodeled it so that it can be done. Further, an irradiation step was added after heating and drying so that the active energy rays could be irradiated as needed.
Table 3 below shows the drying conditions of Examples 1-41 and Comparative Example 1-6.

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

<Substrate adhesion>
The solid portion of the obtained image was evaluated by counting the number of remaining squares of 100 test squares by a grid peeling test using a cloth adhesive tape (123LW-50 manufactured by Nichiban).
The evaluation criteria are as follows. It is desirable to have a level up to "○" in actual use.
The evaluation results are shown in Table 5.
⊚: Number of remaining cells is 98 or more ○: Number of remaining cells is 90 or more and less than 98 Δ: Number of remaining cells is 70 or more and less than 90 ×: Number of remaining cells is less than 70

<Discharge reliability>
The ejection reliability was evaluated using an inkjet printer (IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.). The IPSiO GXe5500 remodeling machine is a remodeling of the IPSiO GXe5500 machine so that printing equivalent to a printing speed of 30 m ² / hr can be reproduced in A4 size with a printing width of 150 cm.
First, the ink jet printers were filled with ink, and after confirming that "nozzle omission" did not occur, the inkjet printer was left in an environment of room temperature of 32 ° C. and humidity of 30% for 12 hours. After leaving for 12 hours, a nozzle check pattern was printed on a PVC film without performing cleaning maintenance, the generated "nozzle omission" was counted, and "discharge reliability" was evaluated based on the following evaluation criteria. It is desirable in actual use that the evaluation is "○" or higher. The "nozzle omission" means that the ink is not ejected and the ink image is not drawn normally.
[Evaluation criteria]
◎: Nozzle omission is 0 points ○: Nozzle omission is within 1 point △: Nozzle omission is within 2 points ×: Nozzle omission is within 4 points × ×: Nozzle omission is within 5 points

<Hardness>
The solid portion of the obtained image was pressed using a nanoindenter (HYSITRON, manufactured by Scientificron), and the Vickers hardness H [GPa] was measured from the load when the needle was pushed into the coating film at a depth of 100 μm. "Hardness" was evaluated based on the following evaluation criteria.
[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] ×: 0.05 [GPa] or less

<Scratchability>
100 reciprocating images were rubbed against the solid part of the obtained image using a friction wear tester with a gold width No. 3 and a load of 500 g. "Scratchability" was evaluated based on the following evaluation criteria.
[Evaluation criteria] (visual)
5: No change 4: The color appears on the gold width, but there is no scratch on the image 3: The color appears on the gold width, and the image also has scratches. There is no image peeling 2: The color is reflected on the gold width, and the image is also scratched. There is less than 20% image peeling on the whole. 1: Color is reflected on the gold width, and the image is also scratched. There is image peeling of 20% or more and less than 50% of the whole. 0: Color is reflected on the gold width, and the image is also scratched. There is more than 50% image peeling on the whole.

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

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

<Film thickness>
A cross section of the image was obtained using a guillotine cutter on the solid part of the obtained image.
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 concentrations of the pigment dispersion and the coating were measured as follows.
<Solid content>
It was calculated by weighing about 1 g of the pigment dispersion or the coating liquid on an aluminum dish having a diameter of 5 cm, drying at 105 ° C. for 1 hour, and weighing the residue.

In Examples 1-22, the reaction reagent (reaction initiator or cross-linking agent) inside the coating body discharged from the inkjet head and the polymerization reaction group of the coating body start a cross-linking reaction by an external stimulus, and three-dimensionally. A chemical bond is formed. Therefore, it was excellent in terms of scratch resistance, hardness, water resistance, and alcohol resistance. In addition, since it contains a large amount of solvent, the film thickness is small and the discharge reliability is high.
Comparative Example 1-2 was inferior in scratch resistance, hardness, and alcohol resistance because it did not have a crosslinked structure.

400 Image forming device 401 Image forming device exterior 401c Device body cover 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 unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Japanese Unexamined Patent Publication No. 2013-199602 Japanese Unexamined Patent Publication No. 2012-251062

Claims (9)

An inkjet recording ink containing water, a reaction initiator, a cross-linking agent, or both, and a compound that reacts with the reaction initiator, the cross-linking agent, or both, wherein the reaction initiator, the cross-linking agent, or the same thereof. Both are contained as a resin-coated coating,
The resin of the coating body is a resin having one or more reactive groups selected from a (meth) acryloyl group, a vinyl group, a vinyl ether group, and a mercapto group.
An inkjet recording ink having a volume average particle diameter of 50 nm or more and 500 nm or less and a weight average molecular weight of the resin of 500 or more and 5000 or less. The ink jet recording ink according to claim 1, wherein the compound that reacts with the reaction initiator, the cross-linking agent, or both is the resin of the coating body. The ink for inkjet recording contains a coating body in which a cross-linking agent is coated with a resin, and the resin has a carboxyl group, a hydroxyl group, an amino group, an amide group, and a thiol group as polymerization reaction groups that react with the cross-linking agent. , The inkjet recording ink according to claim 2, which has one or more selected from an epoxy group and a caprolactam group. The ink for inkjet recording contains a coating body in which a reaction initiator is coated with a resin, and the resin contains a (meth) acryloyl group, a vinyl group, a vinyl ether group, etc. as polymerization reaction groups that react with the reaction initiator. The ink for inkjet recording according to claim 2, which has one or more selected from the mercapto groups. The ink jet recording ink according to any one of claims 1-4, which contains two or more kinds of the reaction initiator or the cross-linking agent. The inkjet recording ink according to any one of claims 1-5, wherein the coating film hardness of the printed matter when the image is printed is Vickers hardness of 0.1 GPa or more. The ink jet recording ink according to any one of claims 1 to 6, which contains a coloring material. The coating is a coating in which a reaction initiator, a cross-linking agent, or both, and one or more selected from an inert monofunctional monomer, polyfunctional monomer, oligomer, polymer, and organic solvent are coated with a resin. The ink for inkjet recording according to any one of claims 1-7. A recording method comprising a step of applying the inkjet recording ink according to any one of claims 1-8 to form an image, and a step of applying an external stimulus to the applied inkjet recording ink to cause a curing reaction.

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