JP2017039915A - Ink, inkjet printing method and printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ink which secures appropriate wettability to various substrates such as a polypropylene (PP) film, a polyvinyl chloride vinyl (PVC) film and a polyethylene terephthalate (PET) film, and furthermore can provide an image excellent in scratch resistance.SOLUTION: There is provided the ink which contains water, an organic solvent, a surfactant, and resin particles, and in which the surfactant contains a silicone-based surfactant, and the resin particle contains a polyolefin site-containing polyester-based urethane resin particle.SELECTED DRAWING: None

Description

  The present invention relates to an ink, an inkjet printing method, and a printed matter.

  Inkjet printers have advantages such as low noise, low running cost, and easy color printing, and are therefore widely used in digital homes as digital signal output devices.

In recent years, not only for home use, but also, for example, a technique for forming an image on a packaging material such as food, beverages, daily necessities, etc. has been developed.
In such applications, non-porous recording media such as plastic films are used, and packaging materials that are printed directly on the surface of plastic films (surface printing) are often used because of low packaging costs. Ink has been developed.
In the surface printing, since the printed layer is in direct contact with the printed layer or box of the adjacent package, the printed layer may be scraped by the friction and the printed content may become unclear, so scratch resistance is required. It is done.

  In view of this, there has been proposed an ink that is a one-component type and is an aqueous type, but can obtain a strong coating on the surface of the plastic film (see, for example, Patent Documents 1 to 4).

  The present invention is an ink capable of obtaining an image excellent in scratch resistance while ensuring appropriate wettability with respect to various substrates such as polypropylene (PP) film, polyvinyl chloride (PVC) film, and polyethylene terephthalate (PET) film. The purpose is to provide.

  The ink of the present invention as a means for solving the above problems is an ink containing water, an organic solvent, a surfactant, and resin particles, and the surfactant contains a silicone-based surfactant. The resin particles contain polyolefin moiety-containing polyester urethane resin particles.

  According to the present invention, an image excellent in scratch resistance is obtained while ensuring appropriate wettability to various substrates such as a polypropylene (PP) film, a polyvinyl chloride (PVC) film, and a polyethylene terephthalate (PET) film. Ink can be provided.

FIG. 1 is a schematic diagram illustrating an example of a serial type inkjet printing apparatus. FIG. 2 is a schematic diagram showing an example of the configuration in the main body of the apparatus of FIG.

(ink)
The ink of the present invention is an ink containing water, an organic solvent, a surfactant, and resin particles, wherein the surfactant contains a silicone-based surfactant, and the resin particles contain a polyolefin site-containing polyester. Contains urethane-based resin particles, and further contains a coloring material and other components as necessary.

The present inventors first studied a surfactant capable of obtaining good wettability to a polypropylene (PP) film, a polyvinyl chloride (PVC) film, and a polyethylene terephthalate (PET) film with respect to various surfactants. .
As a result, with the nonionic surfactant, sufficient wettability could not be obtained regardless of the content in the ink. In addition, since the wettability is too high with fluorosurfactants, color boundary blurring occurs, and if the content in the ink is made very small, it becomes difficult to blur, but ejection from the head becomes unstable. I have. On the other hand, it was found that the silicone surfactant can provide good wettability to the substrate.

However, it has been found that when the base material is a polypropylene (PP) film, the silicone-based surfactant has insufficient wettability and the solid image is not sufficiently filled.
Therefore, in the present invention, it has been found that wettability to a substrate such as a polypropylene (PP) film can be controlled by adding a polyolefin resin emulsion to the ink. The reason for this is not clear, but it is thought that the interfacial tension between the ink and the substrate is lowered, so that wetting and spreading are facilitated.
From the above, the present inventors have found out that a silicone surfactant is suitably used.
However, the polyolefin resin is most suitable from the viewpoint of the affinity for the substrate. However, the polyolefin resin has a low coating film hardness due to its structure, resulting in extremely poor fastness of printed matter.
Thus, the present inventors have found that a polyolefin moiety-containing polyester urethane resin in which an olefin skeleton is incorporated into a polyester urethane resin is excellent from the viewpoint of coexistence of scratch resistance and promotion of wettability, and has led to the present invention.

<Resin particles>
As said resin particle, a polyolefin site | part containing polyester-type urethane resin particle is contained, and also other resin particles are contained as needed.
Here, the polyolefin moiety-containing polyester urethane resin means a polyester urethane resin having a polyolefin skeleton in the main chain or side chain, and the polyester urethane resin means a polyurethane resin having a polyester structure. .
As said polyolefin site | part containing polyester-type urethane resin, what was synthesize | combined suitably may be used and a commercial item may be used.

  The polyolefin part-containing polyester urethane resin has a polyolefin part-containing polyester part which is a flexible soft segment and a urethane part which is a hard segment having a strong cohesive energy, and the hard segment is scattered in the soft segment. Form a film. By the balance of these two segments, it can have flexibility, toughness and elasticity, and has excellent adhesion.

There is no restriction | limiting in particular as a method of synthesize | combining the said polyolefin site | part containing polyester-type urethane resin, According to the objective, it can select suitably, For example, it synthesize | combines by the method represented by following Reaction Formula (1) and (2). can do.
Regarding the following reaction formula (1), the polyolefin moiety-containing polyester urethane resin can be synthesized by a urethanization reaction between a diisocyanate and an olefin moiety-containing polyester diol. That is, a polyester-based urethane resin having a polyolefin skeleton in the main chain can be synthesized by, for example, a urethanization reaction between diisocyanate (I) and an olefin moiety-containing polyester diol (II).

In the reaction formula (1), R ₁ represents any group selected from a divalent (cyclo) alkyl group and a (hetero) aryl group for constituting a known diisocyanate.
R ₂ represents any site selected from an alkylene moiety having 2 or more carbon atoms and a bisphenol moiety in the diol residue.
R ₃ represents any one part selected from an alkylene part having 2 or more carbon atoms and an arylene part in the dicarboxylic acid.
However, it is preferable that at least one of R ₂ and R ₃ is an alkylene moiety having 3 or more carbon atoms. The aryl structure-containing moiety is preferably bisphenol. The bisphenol has an elongated molecular structure such as a —CH ₂ — group or —C (Me) ₂ — group that can ensure the rotation of adjacent phenyl rings, and has a structure that does not hinder the appearance of a flexible structure. Those are preferred.

  The molecular weight of the olefin moiety-containing polyester diol (II) is preferably from 100 to 5,000. Further, the molecular weight of the polyolefin moiety-containing polyester urethane resin (III) is preferably 10,000 or more and 1,000,000 or less.

  In the following reaction formula (2), a polyester-based urethane resin having a polyolefin skeleton in the side chain can be synthesized, for example, by a urethanization reaction between diisocyanate (I) and olefin moiety-containing polyester diol (IV).

In the reaction formula (2), R ₁ represents any group selected from a divalent (cyclo) alkyl group and a (hetero) aryl group for constituting a known diisocyanate.
R ₄ represents any site selected from an alkylene moiety having a branched bond having 1 to 6 carbon atoms and a phenylene group-containing moiety having a branched bond in the diol residue.
R ₅ represents any one part selected from an alkylene part having 2 or more carbon atoms and an arylene part in the dicarboxylic acid.
R ₆ represents a hydrocarbon group that can form a branched flexible pendant moiety with R ₄ .

  The molecular weight of the olefin moiety-containing polyester diol (IV) is preferably from 100 to 5,000. The molecular weight of the polyolefin moiety-containing polyester urethane resin (V) is preferably 10,000 or more and 1,000,000 or less.

As a practical synthesis method, for example, the method described in JP-A-10-72562 can be suitably used.
The synthesis of the polyolefin moiety-containing polyester-based urethane resin is, for example, a polyolefin moiety-containing polyester polyol, other polyester polyols optionally used in combination, a polyisocyanate compound, an acidic group and at least two active hydrogen-containing moieties in the molecule. It is preferable to disperse the acid group of the polyurethane resin consisting of the compound having the above and a chain extender in an aqueous medium by neutralizing with a neutralizing agent if necessary.

<< Polyolefin moiety-containing polyester polyol >>
The polyolefin moiety-containing polyester polyol means at least one of polyolefins containing hydroxyl groups at both ends and side chains of the molecule.
The method for producing the polyolefin moiety-containing polyester polyol is not particularly limited, and may be obtained by a method of obtaining a terminal hydroxyl group polyester by performing dehydration condensation polymerization or transesterification reaction between a compound that imparts an olefin group and a dicarboxylic acid. Can do.

  Examples of the compound that imparts an olefin group in the main chain include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol having a number average molecular weight of less than 500, 1,4-butanediol, and 1,3-butanediol. 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, 3 , 3,5-trimethyl-1,6-hexanediol, 1,9-nonanediol, cyclohexyldimethanol, bis (hydroxyethoxy) benzene, low molar adduct of EO or PO with bisphenols, number average molecular weight less than 500 Bisphenol A ethylene oxide De or propylene oxide adduct, bisphenol A, biphenol F, bisphenol AF, bisphenol E, bisphenol M, bisphenol C, bisphenol S and the like. These may be used alone or in combination of two or more.

  Examples of the compound that imparts an olefin group in the side chain include 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and 1,2-octadecanediol. 1,2-alkanediol having 5 to 42 carbon atoms, or glycerol monohexyl ether, glycerol monooctyl ether, glycerol mono-2-ethylhexyl ether, glycerol monodecyl ether, glycerol monododecyl ether, glycerol monooctadecyl ether, etc. Glycerin monoalkyl ether having 6 to 43 carbon atoms, or glycerin hexanoic acid monoester, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester, glyce Ndodekan acid monoesters, such as the number 7 or 44 or less glycerol fatty acid monoesters carbon such as glycerin octadecanoic acid monomethyl ester. These may be used alone or in combination of two or more.

As shown in the reaction formulas (1) and (2), the polyol (diol) is of a diol structure of an olefin moiety-containing polyester, and in order to obtain the diol structure, the polyesterification reaction with a dicarboxylic acid is performed. In this case, it is preferable to use the polyol (diol) in excess of the dicarboxylic acid.
As the polyolefin moiety-containing polyester polyol, for example, it can also be synthesized by a one-shot synthesis method, but after the first shot for polyesterification, the monitored molecular weight and acid value almost reached the expected value, It can also be synthesized by a two-shot synthesis method comprising a second shot to which an excess of diol (for hydroxylation at the molecular end) is added.
The two-shot synthesis method is one of effective methods for obtaining a polyester polyol by condensation of an oxy acid described later.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids having 4 to 10 carbon atoms (adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, etc.), ester-forming derivatives thereof, and aromatic dicarboxylic acids. Examples include acids (phthalic acid, terephthalic acid, isophthalic acid, etc.) or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

<< Polyester polyol >>
Examples of the polyester polyol include those obtained by esterification of low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and co-polymers thereof. Examples thereof include polymerized polyester. These may be used alone or in combination of two or more.
Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used alone or in combination of two or more.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

  Other raw materials and acquisition methods for polyester-based urethane resins in the present invention are obtained not only by reaction between diol and dicarboxylic acid, but also by condensation of oxyacids having a hydroxy group and a carboxy group simultaneously in one molecule. be able to.

<< Polyisocyanate compound >>
The polyisocyanate compound is not particularly limited. For example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4 '-Diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl Aromatic polyisocyanate compounds such as -4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethyle Diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis ( Aliphatic polyisocyanate compounds such as 2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate; isophorone diisocyanate (IPDI), 4, 4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) ) -4 Jikurohekisen 1,2-dicarboxylate, 2,5-norbornane diisocyanate, and alicyclic polycyanate compound such as 2,6-norbornane diisocyanate Natick sulfonates and the like. These may be used alone or in combination of two or more.
Among these, it is preferable to use an aliphatic or alicyclic diisocyanate compound from the viewpoint of forming a coating film having long-term weather resistance.

<< Compound having an acidic group and at least two active hydrogen-containing sites in the molecule >>
Examples of the compound having an acidic group and at least two active hydrogen-containing sites in the molecule include glycolic acid, tartaric acid, 4,6-dihydroxyisophthalic acid, α, α-dimethylolpropionic acid, α, α-dimethylol. Hydroxy acids such as butyric acid, α, α-dimethylol nonanoic acid, and carboxy group-containing polycaprolactone diol obtained by addition polymerization of caprolactone monomers thereto, hydroxysulfonic acids such as 1,7-dihydroxynaphthalenesulfonic acid, or 2 And aminosulfonic acid such as 4-diaminobenzenesulfonic acid. These may be used alone or in combination of two or more.
Of these, α, α-dimethylolpropionic acid, α, α-dimethylolbutyric acid, which is a compound having two hydroxyl groups and one carboxy group in the molecule, and addition polymerization of these with caprolactone monomer are obtained. Carboxy group-containing polycaprolactone diols are preferred.

<< Chain extender >>
Examples of the chain extender include polyamines and other active hydrogen atom-containing compounds.
Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamine, polyamines such as diethylenetriamine, dipropylenetriamine, and triethylenetetramine, hydrazines such as hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, succinic dihydrazide, and adipic acid dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide. These may be used alone or in combination of two or more.

<< Neutralizer >>
There is no restriction | limiting in particular as said neutralizing agent, According to the objective, it can select suitably, For example, ammonia, an organic amine, etc. are mentioned. These may be used alone or in combination of two or more.

  The polyolefin site-containing polyester urethane resin particles used in the ink of the present invention can be obtained by a conventional and generally used production method, and examples thereof include the following methods.

First, in the absence of a solvent or in the presence of an organic solvent, two types of the polyolefin moiety-containing polyol and polyester polyol and the polyisocyanate compound are reacted at an equivalent ratio in which an isocyanate group becomes excessive, whereby an isocyanate-terminated urethane prepolymer is obtained. To manufacture.
The ratio of (polyester polyol / polyolefin moiety-containing polyol) in the isocyanate-terminated urethane prepolymer is preferably 1.5 or more, more preferably 4 or more, and particularly preferably 9 or more in terms of the molecular weight ratio of each polyol-derived moiety. .
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with the neutralizing agent as necessary, and then reacted with the chain extender, and finally the organic solvent in the system is optionally removed. It can be obtained by removing.
Examples of the anionic group include a carboxy group and a sulfonic acid group. When the anionic group is used, good water dispersion stability can be obtained.
In order to introduce the anionic group into the resin, a monomer having the anionic group can be used.

  The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and acetate esters such as ethyl acetate and butyl acetate. , Nitriles such as acetonitrile, amides such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone. These may be used alone or in combination of two or more.

The volume average particle diameter of the resin particles is preferably 10 nm to 1,000 nm, more preferably 10 nm to 500 nm, and particularly preferably 10 nm to 200 nm.
Here, the volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

In the ink of the present invention, other resin particles can be used in combination with the polyolefin site-containing polyester-based urethane resin particles as necessary.
Examples of the other resin particles include urethane resin particles, polyester resin particles, acrylic resin particles, vinyl acetate resin particles, styrene resin particles, butadiene resin particles, styrene-butadiene resin particles, and vinyl chloride resin. Examples thereof include particles, acrylic styrene resin particles, and acrylic silicone resin particles. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as said other resin particle, What was synthesize | combined suitably according to the objective may be used, and a commercial item may be used. Examples of the commercially available products include Microgel E-1002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.), E-5002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.), and Boncoat 4001 (acrylic). Resin particles, manufactured by DIC Corporation, Boncoat 5454 (styrene-acrylic resin particles, manufactured by DIC Corporation), SAE-1014 (styrene-acrylic resin particles, manufactured by Nippon Zeon Corporation), Cybinol SK-200 (acrylic) Resin particles, manufactured by Syden Chemical Co., Ltd., Primal AC-22, AC-61 (acrylic resin particles, manufactured by Rohm and Haas), Nanoacryl SBCX-2821 (acrylic silicone resin particles, Toyo Ink Manufacturing Co., Ltd.) Made), 3690 (acrylic silicone resin particles) Manufactured by Toyo Ink Mfg. Co., Ltd.), # 3070 (methyl methacrylate polymer resin particles, manufactured by Mikuni Color Ltd.). These may be used alone or in combination of two or more.

The resin emulsion may contain a dispersant such as a surfactant as necessary. As the resin emulsion, a self-emulsifying emulsion is preferable from the viewpoint that it is easy to obtain an ink having a better coating film performance.
As the surfactant, an acid value of the surfactant is preferably 5 mgKOH / g or more and 100 mgKOH / g or less, and preferably contains an anionic group. Further, the acid value is 5 mgKOH / g or more and 50 mgKOH / g. It is especially preferable that it is g or less.
When the surfactant is used, water dispersibility is improved, and when the acid value is 5 mgKOH / g or more and 50 mgKOH / g or less, scratch resistance and chemical resistance can be improved.

The content of the polyolefin-containing polyester urethane resin particles is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass with respect to the total amount of the ink. % To 9% by mass is more preferable, and 5% to 9% by mass is particularly preferable. When the content is 0.1% by mass or more and 20% by mass or less, the fixability of the ink and the stability of the ink are improved, the smoothness of the printing layer is improved, and high glossiness can be obtained. Further, the fixing property to the substrate and the scratch resistance can also be improved.
Moreover, as content of the said polyolefin site | part containing polyester-type urethane resin with respect to the said surfactant whole quantity, it is preferable that it is 0.6 to 90 mass% in conversion of mass.

<Surfactant>
As said surfactant, a silicone type surfactant is contained, and also other surfactant is included as needed.
The silicone-based surfactant is preferably a polyether-modified polysiloxane compound from the viewpoint of reducing the surface tension of the ink and ensuring excellent wettability on a highly hydrophobic non-porous substrate.
As the polyether-modified polysiloxane compound, compounds represented by the following general formula (1) and the following general formula (3) are preferably used.

In the general formula (1), R ₄ and R ₅ represent an alkyl group having 1 to 6 carbon atoms, and X ₁ and X ₂ represent a polyether (polyoxyalkylene) group represented by the following general formula (2). In the general formula (1), a represents an integer of 10 to 80.

In the general formula (2), R ₆ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a (meth) acryl group, EO represents an ethylene oxide group, and PO represents a propylene oxide group. b represents an integer of 1 or more, c represents an integer of 0 or more, and b + c represents an integer of 1 to 30. The order of EO and PO may be random.

In the general formula (3), R ₇ and R ₈ represent an alkyl group having 1 to 6 carbon atoms, and X ₃ represents a polyether (polyoxyalkylene) group represented by the following general formula (4). In the general formula (3), d and e represent an integer of 1 or more, and d + e represents an integer of 2 or more and 50 or less.

In the general formula (4), R ₉ represents an alkyl group having 1 to 6 carbon atoms, R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, EO represents an ethylene oxide group, and PO represents Represents a propylene oxide group. f represents an integer of 1 or more, g represents an integer of 0 or more, and f + g represents an integer of 1 to 30. The order of EO and PO may be random.

  As the silicone-based surfactant represented by the general formula (1), a commercially available product can be used. Examples of the commercially available product include BY16-201 manufactured by Toray Dow Corning Co., Ltd., SF8427, and Big Chemie. Examples include BYK-333 and BYK-UV3500 manufactured by Evonik Degussa, TEGO Glide 410, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, and TEGO Glide 450. These may be used alone or in combination of two or more.

  As the silicone surfactant represented by the general formula (3), a commercially available product can be used. Examples of the commercially available product include SF8428, FZ-2162, 8032ADDITIVE manufactured by Toray Dow Corning Co., Ltd. SH3749, FZ-77, L-7001, L-7002, FZ-2104, FZ-2110, FZ-2123, SH8400, SH3773M, BYK-345, BYK-346, BYK-347, BYK-348, manufactured by BYK Chemie TEGO WET 250, TEGO WET 260, TEGO WET 270, TEGO WET 280 manufactured by Evonik Degussa, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF- manufactured by Shin-Etsu Chemical Co., Ltd. 615A, KF-640, Examples thereof include KF-642 and KF-643. These may be used alone or in combination of two or more.

  The silicone surfactant selected from at least one of the general formulas (1) and (3) may be used alone or in combination of two or more.

  The content of the surfactant is preferably 0.04% by mass or more and 5.1% by mass or less, more preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass with respect to the total amount of the ink. The content is more preferably 3% by mass or less, particularly preferably 0.2% by mass or more and 3.0% by mass or less, and most preferably 0.5% by mass or more and 2% by mass or less. When the content is 0.04% by mass or more and 5.1% by mass or less, the wettability with respect to various base materials becomes optimal, so that good image quality can be obtained.

<Organic solvent>
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, A water-soluble organic solvent is preferable. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl- Polyhydric alcohols such as 1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methyl Amides such as formamide and N, N-dimethylformamide, amines such as monoethanolamine, diethanolamine and triethylamine, dimethylsulfo Sid, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and the like ethylene carbonate. These may be used alone or in combination of two or more.

  As the water-soluble organic solvent, 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol are particularly preferable. When the water-soluble organic solvent is used, the film-forming property of the resin can be improved, the aggregation of the resin particles can be prevented, and the adhesion can be improved.

As content of the said organic solvent with respect to the whole ink, 20 mass% or more and 70 mass% or less are preferable, and 30 mass% or more and 60 mass% or less are more preferable.
When the content of the organic solvent is 20% by mass or more, it becomes difficult to dry the ink, and sufficient ejection stability is easily obtained. It is easy and preferable.

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

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

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

  A method for dispersing the pigment in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a method for forming a resin-coated pigment dispersion in which part or the whole of the pigment surface is wrapped with a polymer is used. , A method of making a self-dispersing pigment that imparts a hydrophilic group to the pigment surface with a hydrophilic group-imparting agent, and a method of making an activator-dispersed pigment that is dispersed by adsorbing the pigment dispersant onto the surface of the pigment. It is done.

<Additives>
If necessary, additives such as antiseptic / antifungal agents, rust preventives, pH adjusters may be used for the ink.

<< antiseptic and antifungal agent >>
The antiseptic / antifungal agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, Examples include sodium chlorophenol, sodium 2-pyridinethiol-1-oxide, and the like.

<< rust preventive agent >>
The rust inhibitor is not particularly limited and may be appropriately selected depending on the intended purpose.For example, acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, Examples include dicyclohexylammonium nitrite.

<< pH adjuster >>
The pH adjuster is not particularly limited as long as it can adjust the pH to a desired value without adversely affecting the ink, and can be appropriately selected according to the purpose. For example, lithium hydroxide, hydroxide Hydroxides of alkali metal elements such as sodium and potassium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, quaternary ammonium hydroxides and amines such as diethanolamine and triethanolamine, hydroxylation Examples include ammonium and quaternary phosphonium hydroxide.

The ink of the present invention is prepared by dispersing or dissolving the above-described constituents in an aqueous medium, and further stirring and mixing as necessary.
The apparatus that can be used for the stirring and mixing is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a stirrer using a normal stirring blade, a magnetic stirrer, and a high-speed disperser. .

(Inkjet printing method and inkjet printing apparatus)
Here, the ink jet printing method of the present invention will be described. The ink jet printing method of the present invention further includes a heating step of applying either thermal energy or mechanical energy to the ink to cause the ink to fly to print an image on a recording medium, and heating the printed matter after printing. Including. The inkjet printing method of the present invention can be preferably carried out by the inkjet printing apparatus.

An ink jet printing apparatus capable of printing using the ink of the present invention will be described with reference to the drawings. In addition, although the case where paper is used is demonstrated, it can print similarly also with respect to another porous base material and a non-porous base material. Inkjet printing apparatuses include a serial type (shuttle type) scanned by a carriage and a line type equipped with a line type head. FIG. 1 is a schematic diagram illustrating an example of a serial type inkjet printing apparatus. .
The ink jet printing apparatus includes an apparatus main body 101, a paper feed tray 102 mounted on the apparatus main body 101, a paper discharge tray 103, and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201. Reference numeral 111 denotes an upper cover, and reference numeral 112 denotes a front surface of the front cover.

In the apparatus main body 101, as shown in FIG. 2, a carriage 133 is slidably held in the main scanning direction by guide rods 131 and stays 132, which are guide members horizontally mounted on left and right side plates (not shown). The scanning is moved by a main scanning motor (not shown).
The carriage 133 has a plurality of ink ejection openings of a print head 134 including four inkjet printing heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

The inkjet printing head constituting the print head 134 includes a piezoelectric actuator such as a piezoelectric element, a thermal actuator that utilizes a phase change caused by liquid film boiling using an electrothermal transducer such as a heating resistor, and a metal phase caused by a temperature change. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
In addition, each sub tank 135 for supplying ink of each color to the print head 134 is mounted on the carriage 133. The sub tank 135 is supplied with ink according to the ink set of the present invention from the ink cartridge 201 of the present invention loaded in the ink cartridge loading section 104 via an ink supply tube (not shown).

On the other hand, as a sheet feeding unit for feeding the substrate 142 loaded on the substrate loading unit (pressure plate) 141 of the sheet feeding tray 102, the substrate 142 is separated and fed one by one from the substrate loading unit 141. Opposite the half-moon roller [paper feed roller 143] and the paper feed roller 143, a separation pad 144 made of a material having a large friction coefficient is provided, and this separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the base material 142 fed from the paper feed unit on the lower side of the print head 134, a transport belt 151 for electrostatically attracting and transporting the base material 142, and a paper feed unit On the conveyor belt 151, the counter roller 152 for transporting the base material 142 fed through the guide 145 with the transport belt 151 being sandwiched between the counter roller 152 and the base material 142 fed substantially vertically upward is changed by about 90 °. And a leading end pressure roller 155 urged toward the conveyor belt 151 by a pressing member 154, and charging as charging means for charging the surface of the conveyor belt 151. A roller 156 is provided.

  The conveyor belt 151 is an endless belt, is stretched between a heater-type conveyor roller 157 and a tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a non-porous substrate adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE). And a back layer (medium resistance layer, earth layer) which is made of the same material as the surface layer and is subjected to resistance control by carbon. A heater-type guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the print head 134. Note that as a paper discharge unit for discharging the base material 142 printed by the print head 134, a separation claw 171 for separating the base material 142 from the transport belt 151, a paper discharge roller 172, and a paper discharge roller 173, After the substrate 142 is dried with hot air by the fan heater 174, it is output to the sheet discharge tray 103 below the sheet discharge roller 172.

A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the base material 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet printing apparatus, the base material 142 is separated and fed one by one from the paper feeding unit, and the base material 142 fed substantially vertically upward is guided by the guide 145, and the conveyance belt 151, the counter roller 152, It is sandwiched between and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °. At this time, the conveyance belt 157 is charged by the charging roller 156, and the base material 142 is electrostatically attracted to the conveyance belt 151 and conveyed.
Therefore, by driving the print head 134 according to the image signal while moving the carriage 133, the ink droplets are ejected onto the stopped base material 142 to print one line, and the base material 142 is conveyed by a predetermined amount. After that, the next line is printed. Upon receiving a print end signal or a signal indicating that the rear end of the base material 142 has reached the printing area, the printing operation is finished, and the base material 142 is discharged onto the discharge tray 103.

When the ink of the present invention is applied to a non-porous substrate, an image having good wettability and scratch resistance can be obtained.
The non-porous substrate means a substrate having a surface with low water permeability, absorbability, and adsorptivity, and includes a material having a large number of cavities inside and a material not opening to the outside. included. More quantitatively, it refers to a base material 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.

  The non-porous substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a vinyl chloride resin (PVC) film, a polyethylene terephthalate (PET) film, a plastic film such as a polycarbonate film, And a polypropylene (PP) film etc. are preferable.

  The ink of the present invention can perform high image quality printing on the non-porous substrate. However, when a heating step is provided after printing, the residual solvent in the ink coating film is reduced, so that the image quality is higher and the abrasion resistance is higher. It is more preferable to heat the recording medium after printing in order to form an image with high property and adhesion and to be able to cope with high-speed printing conditions.

  Moreover, since it is a printing method which has a heating process after printing, since the film forming of the resin contained in an ink is accelerated | stimulated, since the fastness of printed matter improves further, it is preferable.

There is no restriction | limiting in particular as an apparatus used for the said heating process, According to the objective, it can select suitably, For example, apparatuses, such as forced air heating, radiation heating, conduction heating, high frequency drying, and microwave drying, are mentioned. These may be used alone or in combination of two or more.
The heating temperature in the heating is not particularly limited and can be appropriately selected depending on the purpose. Depending on the type and amount of the water-soluble organic solvent contained in the ink and the minimum film-forming temperature of the resin emulsion to be added Further, it can be changed according to the type of the substrate to be printed.
The heating temperature is preferably 40 ° C. or higher and 120 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower, from the viewpoints of drying property and film forming temperature.

  The ink of the present invention can suitably use an ink jet method, but is not limited to the ink jet method, and other printing methods can be used. For example, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, AKKU coating method, smoothing coating method, microgravure Examples thereof include a coating method, a reverse roll coating method, a four or five roll coating method, a dip coating method, a curtain coating method, a slide coating method, and a die coating method.

(Printed matter)
The printed matter of the present invention is a printed matter having a recording medium and a printed layer on the recording medium, wherein the printed layer contains a coloring material, a silicone-based surfactant, and a polyolefin-containing polyester-based urethane resin. To do.

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

(Preparation Example 1)
<Preparation of black pigment dispersion>
Carbon black from Cabot Corporation: Black Pearls (registered trademark) 1000 (BET specific surface area 343 m ² / g, DBPA absorption 105 mL / 100 g) 100 g of 2.5 N (normative) sodium hypochlorite solution 3,000 mL Then, the mixture was stirred at a temperature of 60 ° C. and a speed of 300 rpm and reacted for 10 hours to carry out an oxidation treatment, thereby obtaining a pigment having a carboxylic acid group attached to the surface of carbon black.
This reaction solution was filtered, and the carbon black separated by filtration was neutralized with an aqueous sodium hydroxide solution and subjected to ultrafiltration.
Subsequently, ultrafiltration by a dialysis membrane was performed using the pigment dispersion and ion-exchanged water, and further ultrasonic dispersion was performed to obtain a black pigment dispersion in which the pigment solid content was concentrated to 20% by mass.

(Preparation Example 2)
<Preparation of cyan pigment dispersion>
Cyan in which pigment solid content was concentrated to 20% by mass in the same manner as in Preparation Example 1, except that instead of using carbon black, Pigment Blue 15: 4 (manufactured by SENSIENT, SMART Cyan 3154BA) was used. A pigment dispersion was obtained.

(Preparation Example 3)
<Preparation of magenta pigment dispersion>
Magenta pigment in which pigment solid content was concentrated to 20% by mass in the same manner as in Preparation Example 1, except that Pigment Red 122 (Pigment Red 122, manufactured by Sun Chemical Co., Ltd.) was used instead of carbon black in Preparation Example 1. A dispersion was obtained.

(Preparation Example 4)
<Preparation of yellow pigment dispersion>
A yellow pigment dispersion in which the pigment solid content was concentrated to 20% by mass in the same manner as in Preparation Example 1, except that instead of using carbon black, Pigment Yellow 74 (manufactured by SENSIENT, SMART Yellow 3074BA) was used. Got the body.

(Preparation Example 5)
<Preparation of polyolefin moiety-containing polyester urethane resin emulsion A>
618 parts by mass of polyester diol [1] synthesized by the same method as described in Synthesis Example 1 of JP-A-10-72562 in a pressure polymerization reactor equipped with a thermometer and a stirrer, 1, 4 -19 parts by weight of butanediol, 102 parts by weight of dimethylolpropionic acid, 290 parts by weight of isophorone diisocyanate (IPDI), and 670 parts by weight of acetone were added and reacted at 80 ° C. for 10 hours with stirring, with an isocyanate content of 0 An acetone solution of 20% by mass of an isocyanate-terminated polyurethane resin was obtained. The acetone solution was cooled to 30 ° C., and 42 parts by mass of 28% by mass aqueous ammonia was added. Next, 1,515 parts by mass of water was added to the acetone solution, and acetone was removed at 50 ° C. to 60 ° C. under reduced pressure to obtain a resin emulsion having a solid content of 40.0% by mass and a viscosity of 660 cP / 25 ° C. The number average molecular weight (hereinafter the same) of this resin measured by gel permeation chromatography (GPC) was 15,000. The obtained resin emulsion was dispersed with a paint conditioner (Red Devil, speed adjustable within the range of 50 to 1,425 rpm), and a polyolefin part-containing polyester having a solid content concentration of 40.0% by mass and a volume average particle size of 32 nm. A urethane resin emulsion A was obtained.
In addition, the volume average particle diameter of the resin particles in the obtained polyolefin part-containing polyester-based urethane resin emulsion A was measured using a particle size analyzer (Microtrac Model UPA 9340, manufactured by Nikkiso Co., Ltd.).

(Preparation Example 6)
<Preparation of Polyolefin-Surface-Containing Polyester Urethane Resin Emulsion B>
A separable flask equipped with a stirrer, a dropping funnel with two pressure equalizing tubes, a thermometer, and a water-cooled condenser has an ethylene component content of 48 mol%, a number average molecular weight (Mn) of 3600 g / mol, and a weight average molecular weight. 166.91 g of an ethylene / propylene copolymer having a (Mw) / number average molecular weight (Mn) of 1.65 was charged and nitrogen substitution was performed.
Then, after heating up to 160 ° C., 490.60 g of light acrylate HOB-A (manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxybutyl acrylate) weighed in a dropping funnel at 160 ° C., and 10.71 g of excess Di (tert-butyl oxide) (manufactured by Katayama Chemical Co., Ltd.) was added dropwise over 2 hours.
After dropping, the reaction was carried out at 160 ° C. for 2 hours, then the temperature was raised to 170 ° C., and a reduced pressure treatment was carried out for 3 hours under the conditions of 170 ° C. and 1.33 kPa or less to obtain polyolefin part-containing polyol A. It was.
Next, in a reaction vessel into which a stirrer, a reflux condenser, and a thermometer were inserted, 1,500 g of polylite OD-X-2420 (manufactured by DIC Corporation, polyester polyol), 200 g of the polyolefin moiety-containing polyol A, 2, 2 -220 g of dimethylolpropionic acid (DMPA) and 1,347 g of N-methylpyrrolidone (NMP) were charged in a nitrogen atmosphere and heated to 60 ° C to dissolve DMPA. Next, 1,445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) are added and heated to 90 ° C., and a urethanization reaction is performed over 5 hours. Obtained. The reaction mixture was cooled to 80 ° C., and 4,340 g was extracted from the mixture in which 149 g of triethylamine was added and mixed, and added to a mixed solution of 5,400 g of water and 15 g of triethylamine with vigorous stirring. Next, 1,500 g of ice was added, and 626 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid content concentration became 30% by mass. Then, a dispersion treatment was performed in the same manner as in Preparation Example 5 to obtain a polyolefin part-containing polyester urethane resin emulsion B having a volume average particle diameter of 121 nm of resin particles.

(Preparation Example 7)
<Preparation of polyolefin moiety-containing polyether urethane resin emulsion>
In Preparation Example 6, instead of using Polylite OD-X-2420, the solid concentration was changed in the same manner as Preparation Example 6 except that it was changed to Hiflex D2000 (Daiichi Kogyo Seiyaku Co., Ltd., polyether polyol). A polyolefin part-containing polyether urethane resin emulsion having 30% by mass and a volume average particle diameter of resin particles of 58 nm was obtained.

(Preparation Example 8)
<Preparation of polyester urethane resin emulsion>
In Preparation Example 6, a polyester-based urethane resin emulsion having a solid content concentration of 30% by mass and a volume average particle size of resin particles of 44 nm was obtained in the same manner as Preparation Example 6 except that the polyolefin moiety-containing polyol A was not used.

(Preparation Example 9)
<Preparation of polyolefin resin emulsion>
Propylene-based random copolymer (propylene: ethylene = 96: 4) produced using a metallocene catalyst as a polymerization catalyst is supplied to a twin-screw extruder with a barrel temperature of 35 ° C. for thermal degradation. A polymer was obtained.
100 parts by weight of the degenerated propylene random copolymer, 4 parts by weight of methyl methacrylate, 4 parts by weight of ethyl hexyl acrylate, 3 parts by weight of dicumyl peroxide are mixed in advance and then supplied to a twin-screw extruder. Residence time 5 minutes, rotation speed 300 rpm, barrel temperature 120 ° C. (first and second barrels), 180 ° C. (third and fourth barrels), 100 ° C. (fifth barrel), 130 ° C. (sixth-fourth) The reaction was carried out under the conditions of 8 barrels) to obtain an acrylate-polyolefin copolymer.
Next, in a 2 L four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 200 g of the obtained acrylate-polyolefin copolymer and 35 g of a surfactant (polyoxyethylene alkylamine) Then, 8 g of stearyl glycidyl ether and 36 g of toluene were added and kneaded at 120 ° C. for 30 minutes.
Thereafter, 8 g of 2-amino-2-methyl-1-propanol was added over 5 minutes, held for 5 minutes after the addition, and then 970 g of high purity water heated to 90 ° C. was added over 40 minutes.
After distilling off the toluene by vacuum treatment, the mixture was gradually cooled to room temperature with stirring, the water content was adjusted so that the solid concentration was 40% by mass, and the dispersion treatment was performed in the same manner as in Preparation Example 5, A polyolefin resin emulsion having a volume average particle size of 140 nm of resin particles was obtained.

(Preparation Example 10)
<Preparation of acrylic resin emulsion>
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. The internal temperature is kept at 70 ° C., 4 g of potassium persulfate is added as a polymerization initiator, and after dissolution, 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 365 g of styrene, 545 g of butyl acrylate, and 10 g of methacrylic acid are stirred in advance. The emulsion thus obtained was continuously dropped into the reaction solution over 4 hours, and after completion of the dropping, aging was performed for 3 hours.
After cooling the obtained aqueous liquid to room temperature, ion-exchanged water and sodium hydroxide aqueous solution were added to adjust the solid content concentration to 30% by mass and pH 8, and the dispersion treatment was performed in the same manner as in Preparation Example 5 to obtain a resin. An acrylic resin emulsion having a volume average particle diameter of 100 nm was obtained.

Example 1
-Manufacture of ink 1-
After the mixed liquid of the following formulation is stirred and mixed uniformly, 20% by mass of the black pigment dispersion prepared in Preparation Example 1 is added, and the remaining amount of ion-exchanged water is added so that the total amount becomes 100% by mass. , Stirred.
Thereafter, pressure filtration was performed with a cellulose acetate membrane filter to remove coarse particles, whereby ink 1 was obtained.
[Prescription of mixed solution]
・ Polyolefin moiety-containing polyester-based urethane resin A emulsion: 15% by mass
・ BY16-201 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.5% by mass
・ 1,2-propanediol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 30% by mass
・ Proxel LV ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1% by mass

(Preparation of Examples 2 to 16 and Comparative Examples 1 to 7)
Inks of Examples 2 to 16 and Comparative Examples 1 to 7 were obtained in the same manner as in Example 1 except that the composition in Example 1 was changed to Tables 1-1 to 1-3.

Details of each component of the inks in Table 1-1 to Table 1-3 are as follows.
* BY16-201: polyether modified polysiloxane surfactant manufactured by Toray Dow Corning Co., Ltd. * BYK-333: polyether modified polysiloxane surfactant manufactured by Big Chemie Japan * WET-250: Evonik Degussa Polyether modified siloxane copolymer, substrate wetting agent (surfactant)
* KF-351A: Polysiloxane surfactant manufactured by Shin-Etsu Chemical Co., Ltd. * FS-300: Fluorosurfactant manufactured by Deyupon, ZONYL FS-300 (active ingredient: 40% by mass)
* EP-5035: Nonionic surfactant manufactured by Nippon Shokubai Co., Ltd. * Proxel LV: Antiseptic / antifungal agent manufactured by Abyssia

[Evaluation of ink]
About the produced ink of each Example and a comparative example, the following wettability evaluation, solid embedding evaluation, solid embedding evaluation, and abrasion resistance evaluation were implemented. The results are shown in Table 2.

The manufacturer names and grades of various films used in ink evaluation are as follows.
PVC film: 3M D-JET2
PET film: Espet E5100 manufactured by Toyobo Co., Ltd.
PP film: Pyrene P2102 manufactured by Toyobo Co., Ltd.

<Brightness evaluation>
After filling the prepared ink into an ink jet printer (Ricoh Co., Ltd., IPSIO GXe5500) and printing an image sample consisting of only a single-colored character with no background on various films of PVC film, PET film, and PP film And dried at 80 ° C. for 1 hour.
The size of the printed character was set to 11 points with an MS Gothic font, visually confirmed, and “brightness” was evaluated according to the following criteria.
In addition, C evaluation or more is a level which does not have a problem in use.
[Evaluation criteria]
A: There is almost no blurring and the characters are clear. B: Slight blurring has occurred, but the characters can be read sufficiently. C: Obviously there are blurring, but the characters can be read. D: Clearly Blemish occurs and it is difficult to read the characters

<Evaluation of solid filling>
The prepared ink was filled into an ink jet printer (manufactured by Ricoh Co., Ltd., IPSIO GXe5500), and a solid image was printed on various films of PVC film, PET film, and PP film at an ink adhesion amount of 1 mg / cm ² , and then 80 Dry at 1 ° C. for 1 hour.
Next, the printed solid image was observed at a magnification of 20 times using a microscope (manufactured by Keyence Co., Ltd., VHX-200). The ratio was measured and evaluated according to the following criteria.
In addition, C evaluation or more is a level which does not have a problem in use.
[Evaluation criteria]
A: The ink adhesion area is greater than 97% B: The ink adhesion area is greater than 95% and is 97% or less C: The ink adhesion area is 92% or more and 95% or less D: The ink adhesion area is less than 92%

<Evaluation of scratch resistance of image>
The prepared ink was filled in an ink jet printer (manufactured by Ricoh Co., Ltd., IPSIO GXe5500), a solid image was printed on a PP film at an ink adhesion amount of 1 mg / cm ² , and then dried at 80 ° C. for 1 hour. Next, the printed solid image was rubbed with a dry cotton (Kanakin No. 3) under a load of 400 g, visually confirmed, and scratch resistance was evaluated according to the following criteria.
In addition, C evaluation or more is a level which does not have a problem in use.
[Evaluation criteria]
A: The image does not change even after rubbing 50 times or more B: Some scratches remain after rubbing 50 times, but it does not affect the image quality, and there is no problem in actual use C: The image is scratched 31 to 50 times Deterioration of image quality D: Image quality is degraded during rubbing 11 to 30 times E: Image quality is degraded by rubbing 10 times or less

  Examples 1 to 4 are particularly preferred examples of the present invention. For various substrates such as polypropylene (PP) film, polyvinyl chloride (PVC) film, and polyethylene terephthalate (PET) film which are non-porous recording media. It can be seen that good wettability (brightness evaluation and solid embedding evaluation) and good scratch resistance are obtained.

Comparative Example 1 is an example in which a fluorosurfactant was used. In particular, the blurring in the PVC film and the PET film was severe, and the characters were not readable on the PET film.
Comparative Example 2 was an example using a nonionic surfactant, and the solid filling property was poor and was a conspicuous level.
Comparative Examples 3 and 4 are urethane resins, but are Comparative Example 3 using a polyolefin-based polyether-based urethane resin emulsion and Comparative Example 4 using an unmodified polyester-based urethane resin emulsion, both of which are actually used. As a result, the scratch resistance was inferior enough to withstand.
Comparative Example 5 is an example using a polyolefin resin emulsion. In addition to being inferior in scratch resistance, compatibility with the PP film was too good and the blurring in the PP film was greatly deteriorated.
Comparative Example 6 is an example using an acrylic resin emulsion. In addition to being inferior in scratch resistance, the affinity for the PP film was low and the solid filling property in the PP film was greatly deteriorated.
Comparative Example 7 is an example that does not contain resin particles. Since only the pigment is placed on the substrate, there is no scratch resistance, and the liquid droplets do not solidify, so that the blurring is also deteriorated.
In consideration of the use for outdoor use, the adhesion of the base material was evaluated by a general method assuming outdoor use. From these evaluation results, the ink of the present invention is suitable for outdoor use. You can see that

(Test Example 1)
<Evaluation of effects in heat drying>
In the ink 1 of Example 1, as shown in Table 3 below, in the same manner as in Example 1 except that the heating conditions after recording (the heating temperature after printing and the drying time) were changed, The embedding property and scratch resistance were evaluated. The results are shown in Table 3.
In Test Example 1, a solid image was printed in the same manner as in Example 1, and dried without heating after printing (25 ° C., left overnight).

As an aspect of this invention, it is as follows, for example.
<1> An ink containing water, an organic solvent, a surfactant, and resin particles,
The surfactant contains a silicone surfactant,
The ink is characterized in that the resin particles contain polyolefin-containing polyester-based urethane resin particles.
<2> The ink according to <1>, further including a color material.
<3> The ink according to any one of <1> to <2>, wherein the silicone-based surfactant is a polyether-modified polysiloxane compound.
<4> The ink according to any one of <1> to <3>, wherein a content of the silicone surfactant is 0.05% by mass or more and 5% by mass or less.
<5> The ink according to any one of <1> to <4>, wherein the content of the silicone surfactant is 0.1% by mass or more and 3% by mass or less.
<6> The organic solvent according to any one of <1> to <5>, wherein the organic solvent contains at least one selected from 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol. The ink described.
<7> The ink according to any one of <1> to <6>, wherein the content of the organic solvent is 20% by mass or more and 70% by mass or less.
<8> The polyolefin moiety-containing polyester-based urethane resin particles include a polyolefin moiety-containing polyester polyol, a polyester polyol, a polyisocyanate compound, a compound having an acidic group and at least two active hydrogen-containing moieties in the molecule, and a chain. The ink according to any one of <1> to <7>, which is synthesized from an extender.
<9> The ink according to <8>, wherein the polyolefin moiety-containing polyester polyol contains a structural unit derived from bisphenol in a molecule.
<10> The ink according to any one of <8> to <9>, wherein the polyisocyanate compound is at least one selected from aliphatic diisocyanate and alicyclic diisocyanate.
<11> A compound having an acidic group and at least two active hydrogen-containing sites in the molecule is obtained by addition polymerization of α, α-dimethylolpropionic acid, α, α-dimethylolbutyric acid, and caprolactone monomer thereto. The ink according to any one of <8> to <10>, wherein the ink is at least one selected from carboxy group-containing polycaprolactone diols.
<12> The ink according to any one of <1> to <11>, wherein the content of the polyolefin moiety-containing polyester urethane resin particles is 1% by mass or more and 9% by mass or less.
<13> The ink according to any one of <1> to <12>, wherein the content of the polyolefin moiety-containing polyester urethane resin particles is 5% by mass or more and 9% by mass or less.
<14> The ink according to any one of <1> to <13>, wherein a content of the polyolefin moiety-containing polyester urethane resin particles with respect to the surfactant is 0.6% by mass or more and 90% by mass or less. is there.
<15> The ink according to any one of <1> to <14>, wherein the polyolefin moiety-containing polyester-based urethane resin particles have a volume average particle diameter of 10 nm to 1,000 nm.
<16> The ink according to any one of <1> to <15>, which is for inkjet.
<17> Printing the image on a recording medium by applying either thermal energy or mechanical energy to the ink according to any one of <1> to <16> to cause the ink to fly. Inkjet printing method.
<18> The inkjet printing method according to <17>, further including a heating step of heating the printed material after printing.
<19> The inkjet printing method according to <18>, wherein the heating temperature in the heating step is 40 ° C. or higher and 120 ° C. or lower.
<20> A printed matter having a recording medium and a printing layer on the recording medium,
The printed layer contains a coloring material, a silicone-based surfactant, and a polyolefin moiety-containing polyester-based urethane resin.

  According to the ink according to any one of <1> to <16>, the ink-jet printing method according to any one of <17> to <19>, and the printed matter according to <20>, The problem can be solved and the object of the present invention can be achieved.

142 Paper 174 Fan heater

JP 2005-220352 A JP 2011-094082 A JP 2010-116459 A Japanese Patent Laid-Open No. 10-72562

Claims (10)

An ink containing water, an organic solvent, a surfactant, and resin particles,
The surfactant contains a silicone surfactant,
The ink according to claim 1, wherein the resin particles contain polyolefin-containing polyester urethane resin particles.   The ink according to claim 1, further comprising a coloring material.   The ink according to claim 1, wherein the silicone-based surfactant is a polyether-modified polysiloxane compound.   The ink according to any one of claims 1 to 3, wherein a content of the silicone surfactant is 0.05% by mass or more and 5% by mass or less.   The ink according to any one of claims 1 to 4, wherein the organic solvent contains at least one selected from 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol.   The ink according to any one of claims 1 to 5, wherein the content of the polyolefin moiety-containing polyester-based urethane resin particles is 1% by mass or more and 9% by mass or less.   The ink according to any one of claims 1 to 6, which is used for inkjet.   8. An ink jet printing method, wherein either one of thermal energy and mechanical energy is applied to the ink according to claim 1 to cause the ink to fly to print an image on a recording medium.   The inkjet printing method according to claim 8, further comprising a heating step of heating the printed material after printing. A printed matter having a recording medium and a printing layer on the recording medium,
The printed layer contains a color material, a silicone-based surfactant, and a polyolefin moiety-containing polyester-based urethane resin.