JP2017075291A - Ink, and inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide ink having excellent adhesion to various base materials including a non-permeable base material such as polypropylene.SOLUTION: The present invention provides ink comprising water, a colorant, an organic solvent, and a resin, the organic solvent including 1-methoxy-2-propanol, the resin including polyester urethane resin having a polyolefin structure. Embodiments are preferable such that the 1-methoxy-2-propanol has a content of 5 mass% or more, and the polyester urethane resin having a polyolefin structure has a content of 2.0 mass% or more and 9 mass% or less.SELECTED DRAWING: None

Description

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

  In recent years, for example, techniques for recording images using ink on packaging materials such as foods, beverages, and daily necessities have been developed.

As the packaging material, a non-permeable base material such as a plastic film is often used. For example, an image is recorded on the back surface of the plastic film with an ink to form a recording layer, and the adhesive is adhered onto the recording layer. An adhesive is applied and a film that can be heat sealed is laminated and laminated.
Among the packaging materials to be laminated, a soft packaging material is inexpensive and has a lot of excellent properties such as moldability, chemical resistance, and heat resistance, so that a polypropylene film is often used. Inks that can be recorded on film have been developed.
However, unlike the synthetic resin having polarity, the polypropylene film is non-polar and has crystallinity, so that there is a problem that the water-based ink is easily repelled and it is difficult to closely adhere the ink layer.

Although the ink containing a chlorinated polyolefin resin is effective for the above problem, the chlorinated polyolefin resin generates a chlorine compound when incinerated. There is a problem that.
Then, the water-based ink composition containing the emulsion of a chlorinated polypropylene or a polypropylene-acryl copolymer is proposed (for example, refer patent document 1).

  An object of this invention is to provide the ink which is excellent in the adhesiveness with respect to various base materials containing non-permeable base materials, such as a polypropylene.

  The ink of the present invention as a means for solving the problems is an ink containing water, a coloring material, an organic solvent, and a resin, wherein the organic solvent contains 1-methoxy-2-propanol, The resin contains a polyester urethane resin having a polyolefin structure.

  According to the present invention, it is possible to provide an ink having excellent adhesion to various substrates including a non-permeable substrate such as polypropylene.

FIG. 1 is a perspective explanatory view showing an example of a serial type image forming apparatus. FIG. 2 is a perspective explanatory view showing an example of a main tank of the apparatus of FIG.

The ink of the present invention contains water, a coloring material, an organic solvent, and a resin, the organic solvent contains 1-methoxy-2-propanol, and the resin contains a polyester urethane resin having a polyolefin structure. Further, it contains other components as required.
In the ink of the present invention, as a packaging material, a film that shrinks the base material itself by heating, a so-called shrink film may be used, and when the ink is applied to the film and dried, the film does not shrink. Therefore, when the ink is dried at a low temperature of about 40 ° C., the conventional water-based ink composition containing an emulsion of chlorinated polypropylene or polypropylene-acrylic copolymer cannot provide adhesion to the substrate. It is based on the knowledge that.
Therefore, the present inventors may first refer to a polypropylene (hereinafter sometimes referred to as “PP”) film, polyethylene terephthalate (hereinafter also referred to as “PET”) as a non-permeable substrate under sufficient heating conditions. A polyester urethane resin having a polyolefin structure, which is a material capable of ensuring sufficient adhesion to a certain film and a nylon (hereinafter also referred to as “ONY”) film, was selected. Next, the effect of adding various organic solvents on adhesion was confirmed. As a result, it was found that a hydrophilic organic solvent having a high solubility parameter (hereinafter also referred to as “SP value”) can improve the adhesion. However, even when a hydrophilic organic solvent having a high SP value (SP value: 13 (cal / cm ³ ) ^1/2 ) is used, in order to improve the adhesion to a non-permeable substrate, ink is used. It was found that a heat treatment of 50 ° C. or more and 60 ° C. or less is necessary for drying. On the other hand, although the mechanism is not clear, 1-methoxy-2-propanol (SP value: 10.2 (cal / cm ³ ) ^1/2 ) was added despite the organic solvent having a low SP value. In the case of drying the ink, it was found that the adhesion to the substrate is specifically secured even at a heat treatment temperature as low as 40 ° C.

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

<Organic solvent>
The organic solvent contains 1-methoxy-2-propanol, and further contains other organic solvents as necessary.

The content of 1-methoxy-2-propanol is preferably 1% by mass or more, and more preferably 5% by mass or more based on the total amount of the ink. Adhesiveness to various base materials can be improved as the content is 1% by mass or more.
The mechanism by which the adhesion to various base materials is promoted by containing the 1-methoxy-2-propanol is not clear, but has the effect of enhancing the film formation by the polyester urethane resin having the polyolefin structure. Guessed.

<< Other organic solvents >>
Examples of the other organic solvents include ethylene glycol (boiling point: 197.3 ° C.), diethylene glycol (boiling point: 244.3 ° C.), 3-methoxy-1-butanol (boiling point: 158 ° C.), and 3-methyl-3. -Methoxy-1-butanol (boiling point: 173 ° C), 1,2-propanediol (boiling point: 188.2 ° C), 1,3-propanediol (boiling point: 214 ° C), 1,2-butanediol (boiling point: 198 ° C.), 1,3-butanediol (boiling point: 207.5 ° C.), 2,3-butanediol (boiling point: 77 ° C.), 3-methyl-1,3-butanediol (boiling point: 116 ° C.), tri Ethylene glycol (boiling point: 278.4 ° C.), polyethylene glycol, polypropylene glycol, 1,5-pentanediol (boiling point: 239 ° C.), 1,6-hexanediol (Boiling point: 250 ° C.), glycerin (boiling point: 290 ° C.), 1,2,6-hexanetriol (boiling point: 178 ° C.), 2-ethyl-1,3-hexanediol (boiling point: 244 ° C.), 1, 2,4-butanetriol (boiling point: 325 ° C), 1,2,3-butanetriol (boiling point: 175 ° C), 3-methylpentane-1,3,5-triol (petriol, boiling point: 216 ° C), etc. Polyhydric alcohols, ethylene glycol monoethyl ether (boiling point: 196 ° C.), ethylene glycol monobutyl ether (boiling point: 171 ° C.), diethylene glycol monomethyl ether (boiling point: 194 ° C.), diethylene glycol monoethyl ether (boiling point: 202 ° C.), Diethylene glycol monobutyl ether (boiling point: 230 ° C), tetraethylene glycol mono Polyhydric alcohol alkyl ethers such as chill ether (boiling point: 275 ° C.), propylene glycol monoethyl ether (boiling point: 132.8 ° C.), ethylene glycol monophenyl ether (boiling point: 237 ° C.), ethylene glycol monobenzyl ether (boiling point: 158 ° C) and the like, 2-pyrrolidone (boiling point: 245 ° C), N-methyl-2-pyrrolidone (boiling point: 204 ° C), N-hydroxyethyl-2-pyrrolidone (boiling point: 309 ° C) 1,3-dimethylimidazolidinone (boiling point: 220 ° C.), ε-caprolactam (boiling point: 136 ° C. to 138 ° C.), γ-butyrolactone (boiling point: 204 ° C.), etc., nitrogen-containing heterocyclic compounds, formamide (boiling point: 210 ° C), N-methylformamide (boiling point: 199 ° C), N, N-dimethyl Amides such as formamide (boiling point: 153 ° C), amines such as monoethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 280 ° C), triethylamine (boiling point: 89.7 ° C), dimethyl sulfoxide (boiling point: 189) ° C), sulfolane (boiling point: 285 ° C), sulfur-containing compounds such as thiodiethanol (boiling point: 164 ° C to 166 ° C), propylene carbonate (boiling point: 242.1 ° C), ethylene carbonate (boiling point: 260.7 ° C), etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because good drying properties can be obtained, and 1,2-propanediol (boiling point: 188.2 ° C.), 1,2-butanediol ( Boiling point: 198 ° C), diethylene glycol monobutyl ether (boiling point: 230 ° C), and 3-methyl-3-methoxy-1-butanol (boiling point: 173 ° C) are more preferable.

  The content of the organic solvent is preferably 1% by mass to 60% by mass, more preferably 5% by mass to 60% by mass, and particularly preferably 10% by mass to 60% by mass with respect to the total amount of the ink. When the content is 1% by mass or more and 60% by mass or less, the ejection stability can be improved. When the content is 1% by mass or more, the ink is difficult to dry and sufficient ejection stability can be improved, and 60% by mass. When it is below, the viscosity can be kept low and the drying property can be improved.

<Resin>
The resin contains a polyester urethane resin having a polyolefin structure, and further contains other resins as necessary.
The polyester urethane resin having a polyolefin structure means a polyester urethane resin having a polyolefin structure in the main chain or side chain, and the polyester urethane resin is a urethane resin obtained by reacting a polyester polyol and a polyisocyanate. Means a polyester-based urethane resin.
In addition to polyester urethane resins, there are polyether urethane resins and polycarbonate urethane resins. Urethane resins must be polyester urethane resins in order to obtain sufficient adhesion to various substrates in actual use. Don't be.
The polyester urethane resin having the polyolefin structure can be structurally analyzed using, for example, a GC-MS apparatus (apparatus name: QP2010, manufactured by Shimadzu Corporation).

As the polyester urethane resin having the polyolefin structure, a newly synthesized one or a commercially available product may be used.
When a polyester urethane resin having a polyolefin structure is newly synthesized, a synthesis method for obtaining a polyester urethane resin having a polyolefin structure is not particularly limited and may be appropriately selected depending on the purpose. Examples include the method described in Kaihei 10-72562. That is, it is obtained by reacting a polyester polyol having an olefin structure, another polyester polyol, a polyisocyanate compound, a compound having an acidic group and at least two active hydrogen-containing groups in the molecule, and a chain extender. The polyester urethane resin having a polyolefin structure can be obtained by neutralizing the acid group of the polyurethane resin with at least one of ammonia and an organic amine and dispersing it in an aqueous medium.

-Polyester polyol having an olefin structure-
The polyester polyol having an olefin structure is a polyester polyol having a polyolefin structure at both ends of a molecule and at least one of side chains.
There is no restriction | limiting in particular as a manufacturing method of the polyester polyol which has the said olefin structure, According to the objective, it can select suitably, For example, the dehydration polycondensation of the compound which provides an olefin group, and dicarboxylic acid, and transesterification Examples include a method of performing at least one of the reactions to obtain a polyester having a hydroxyl group at the terminal.

--Compound that imparts an olefin group--
Examples of the compound that imparts the olefin group include carbon numbers such as 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-octadecanediol, and the like. Is a 1,2-alkanediol having a glycerin monohexyl ether, glycerin monooctyl ether, glycerin mono-2-ethylhexyl ether, glycerin monodecyl ether, glycerin monododecyl ether, glycerin monooctadecyl ether, etc. 6 to 43 glycerin monoalkyl ether; glycerin hexanoic acid monoester, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester, glycerin dodecanoic acid Esters, such as glycerol fatty acid monoester of 7 or more 44 or less carbon atoms such as glycerin octadecanoic acid monomethyl ester. These may be used individually by 1 type and may use 2 or more types together.

--Dicarboxylic acid--
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.), or ester-forming derivatives thereof; aromatic Examples thereof include dicarboxylic acids (phthalic acid, terephthalic acid, isophthalic acid, etc.) or ester-forming derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.

-Other polyester polyols-
There is no restriction | limiting in particular as said other polyester polyol, According to the objective, it can select suitably, For example, what is obtained by esterifying a low average molecular weight polyol and polycarboxylic acid, (epsilon) -caprolactone Examples thereof include polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as these, or copolymerized polyesters thereof. These may be used individually by 1 type and may use 2 or more types together.
Examples of the low average molecular weight polyol include ethylene glycol and propylene glycol. These may be used individually by 1 type and may use 2 or more types together.
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 individually by 1 type and may use 2 or more types together.

-Polyisocyanate compound-
The polyisocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. 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'- Aromatic poly, such as diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate Isocyanate compound; Eth Diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Aliphatic polyisocyanate compounds such as proate, bis (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 TD) ), Alicyclic polycyanate compounds such as bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, an aliphatic polyisocyanate compound and an alicyclic polycyanate compound are preferable from the viewpoint of obtaining a coating film having long-term weather resistance.

-Compounds having an acidic group and at least two active hydrogen-containing groups in the molecule-
The compound having an acidic group and at least two active hydrogen-containing groups in the molecule is not particularly limited and may be appropriately selected depending on the intended purpose. For example, glycolic acid, tartaric acid, 4,6-dihydroxyisophthalate Hydroxy acids such as acid, 2,2-dimethylolpropionic acid, α, α-dimethylolbutyric acid, α, α-dimethylolnonanoic acid, and carboxyl group-containing polycaprolactone diol obtained by addition polymerization of these with caprolactone monomer; Examples thereof include hydroxysulfonic acid such as 1,7-dihydroxynaphthalenesulfonic acid; aminosulfonic acid such as 2,4-diaminobenzenesulfonic acid. These may be used individually by 1 type and may use 2 or more types together. Among these, compounds having two hydroxyl groups and one carboxyl group in the molecule are preferable, and obtained by addition polymerization of 2,2-dimethylolpropionic acid, α, α-dimethylolbutyric acid, and caprolactone monomer thereto. More preferred is a carboxyl group-containing polycaprolactone diol.

-Chain extender-
There is no restriction | limiting in particular as said chain extender, According to the objective, it can select suitably, For example, a polyamine, another active hydrogen atom containing compound, etc. are mentioned.
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 diamines; Polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazines such as hydrazine, N, N′-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Succinic dihydrazide, Adipic dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide. These may be used individually by 1 type and may use 2 or more types together.

[Method for producing polyester urethane resin having polyolefin structure]
There is no restriction | limiting in particular as a manufacturing method of the polyester urethane resin which has the said polyolefin structure, According to the objective, it can select suitably, For example, the following methods etc. are mentioned.

First, in the absence of a solvent or in the presence of an organic solvent, the polyester polyol having the olefin structure, the other polyester polyol, and the polyisocyanate compound are reacted at an equivalent ratio in which an isocyanate group becomes excessive, to obtain an isocyanate. A terminal urethane prepolymer is produced.
The content ratio of the other polyester polyol (A) and the polyester polyol (B) having an olefin structure at this time is 60:40 in terms of the weight average molecular weight ratio (A: B) in the polyol-derived site in the prepolymer. The above is preferable, 80:20 or more is more preferable, and 90:10 or more is particularly preferable.

  Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with a neutralizing agent as necessary, then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. Can be obtained.

  There is no restriction | limiting in particular as an organic solvent which can be used, According to the objective, it can select suitably, For example, Ketones, such as acetone and methyl ethyl ketone; Ethers, such as tetrahydrofuran and dioxane; Acetic acid, such as ethyl acetate and butyl acetate Esters; 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.

As the polyester urethane resin having the polyolefin structure, if necessary, a dispersant such as a surfactant may be contained in the ink, but from the viewpoint of easily obtaining an ink having a better coating film performance, So-called self-emulsifying emulsions are preferred.
The acid value of the self-emulsifying emulsion preferably contains an anionic group in the range of 5 mgKOH / g or more and 100 mgKOH / g or less from the viewpoint of water dispersibility, and has excellent scratch resistance and chemical resistance. It is more preferable that an anionic group is contained in the range of 5 mgKOH / mg to 50 mgKOH / mg.
As the anionic group, for example, when a carboxyl group, a sulfonic acid group, or the like is used, good water dispersion stability can be obtained, and these anionic groups are introduced into the polyester urethane resin having the polyolefin structure. May use monomers having these anionic groups.

  The volume average particle size of the polyester urethane resin having a polyolefin structure is preferably 10 nm or more and 1,000 nm or less, more preferably 10 nm or more and 200 nm or less, and further preferably 10 nm or more and 50 nm or less, particularly from the viewpoint of use in an inkjet recording apparatus. . The volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrack MODEL UPA9340, manufactured by Nikkiso Co., Ltd.).

  The content of the polyester urethane resin having a polyolefin structure is preferably 1% by mass or more and 10% by mass or less from the viewpoint of fixability and ink stability with respect to the total amount of the ink, and the resin is sufficiently oriented to the interface. In addition, from the viewpoint of suppressing the generation of internal stress, 2.0% by mass or more and 9% by mass or less is more preferable.

In addition to the polyester urethane resin having the polyolefin structure, the ink of the present invention may be used in combination with other resins as necessary.
Examples of the other resin include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, and acrylic silicone. Based resins and the like. These may be used individually by 1 type and may use 2 or more types together.

  As said other resin, what was synthesize | combined suitably may be used and a commercial item may be used. Examples of the other commercially available resins include, for example, trade name: Microgel E-1002, trade name: E-5002 (styrene-acrylic resin fine particles, manufactured by Nippon Paint Co., Ltd.), trade name: Boncoat 4001 (acrylic) Type resin fine particles, manufactured by DIC Corporation), trade name: Boncoat 5454 (styrene-acrylic resin fine particles, manufactured by DIC Corporation), trade name: SAE-1014 (styrene-acrylic resin fine particles, manufactured by Nippon Zeon Co., Ltd.), Product name: Cybinol SK-200 (acrylic resin fine particles, manufactured by Seiden Chemical Co., Ltd.), product name: Primal AC-22, product name: Primal AC-61 (acrylic resin fine particles, above, manufactured by Rohm and Haas Co., Ltd.) ), Trade name: Nanoacryl SBCX-2821, trade name: Nanoacryl SBCX-368 (Acrylic silicone resin particles, manufactured by Toyo Ink Co., Ltd.), trade name: # 3070 (methyl polymer resin particles methacrylate, manufactured by Mikuni Color Ltd.). These may be used individually by 1 type and may use 2 or more types together.

  The content of the other resin is preferably 50% by mass or less based on the total amount of the ink. When the content is 50% by mass or less, glossiness and scratch resistance can be improved.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The ink of the present invention is preferably used for inkjet.

[viscosity]
The viscosity of the ink of the present invention is preferably 2 mPa · s or more and preferably 3 mPa · s or more and 20 mPa · s or less at 25 ° C. from the viewpoint of ejection stability and image quality such as character quality when recorded on plain paper. Is more preferable. When the viscosity is 2 mPa · s or more, ejection stability can be improved.

[Production method]
The method for producing the ink of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. For example, water, a coloring material, a resin, an organic solvent, and other components are dispersed or dissolved in an aqueous medium. In addition, a method of stirring and mixing as necessary may be mentioned.
Examples of the stirring and mixing include a stirrer using a normal stirring blade, a magnetic stirrer, and a high-speed disperser.

<Recording medium>
The recording medium used in the present invention can be used without any particular limitation, and plain paper, glossy paper, special paper, cloth, etc. can be used, but it can be particularly preferably used for non-permeable substrates. .
The non-permeable base material means a base material having a surface with low water permeability, absorbability and / or adsorptivity, and includes materials that do not open to the outside even if there are many cavities inside. Meaning, and more quantitatively, means a base material having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.

  Among the non-permeable substrates, good adhesion can be obtained particularly for polypropylene films, polyethylene terephthalate films, and nylon films.

Commercially available products may be used as the polypropylene film. Examples of the commercially available products include trade name: P-2002, trade name: P-2161, trade name: P-4166 (above, manufactured by Toyobo Co., Ltd.). ), Product name: PA-20, product name: PA-30, product name: PA-20W (above, manufactured by Sun Tox Corporation), product name: FOA, product name: FOS, product name: FOR (above, Futamura Chemical Co., Ltd.).
As the polyethylene terephthalate film, a commercially available product may be used. Examples of the commercially available product include trade name: E-5100, trade name: E-5102 (above, manufactured by Toyobo Co., Ltd.), trade name: P60, product. Name: P375 (above, manufactured by Toray Industries, Inc.), product name: G2, product name: G2P2, product name: K, product name: SL (manufactured by Teijin DuPont Films Ltd.), and the like.
As the nylon film, a commercial product may be used. As the commercial product, a trade name: Harden film N-1100, a trade name: Harden film N-1102, a trade name: Harden film N-1200 (or more, Toyobo Co., Ltd.), trade name: ON, trade name: NX, trade name: MS, trade name: NK (manufactured by Unitika Ltd.), and the like.
The ink of the present invention is preferably heat-treated after the ink flying step from the viewpoint that the residual solvent in the ink coating film is reduced and the adhesion to the substrate can be further improved.

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

<Ink cartridge>
The ink cartridge contains ink in a container and further includes other members appropriately selected as necessary.

  The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, an ink bag formed of a plastic container, an aluminum laminate film, etc. And the like.

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

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

The various recording apparatuses (inkjet recording apparatuses) using the ink jet recording method preferably include an ink applying unit that applies a stimulus to the ink and applies the ink to a recording medium.
The recording method (inkjet recording method) preferably includes an ink flying step of recording an image on a recording medium by applying a stimulus to the ink and causing the ink to fly.

The heating step is a step of heating the recording medium on which an image is recorded.
As the recording method, high image quality recording can be performed on the non-permeable substrate, but it is possible to cope with the formation of an image with higher image quality, abrasion resistance and adhesion, and high-speed recording conditions. Therefore, it is preferable to heat the non-permeable substrate after the ink flying step. When the heating step is included after the ink flying step, the film formation of the resin contained in the ink is promoted, so that the image hardness of the recorded matter can be improved.

As the apparatus used for the heating step, many known apparatuses can be used, and examples thereof include forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, and the like. These may be used alone or in combination of two or more.
The heating temperature can be changed according to 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, and also depending on the type of the substrate to be printed. Can be changed.
The heating temperature is preferably 25 ° C. or higher and 45 ° C. or lower, and more preferably 35 ° C. or higher and 45 ° C. or lower from the viewpoints of drying properties and film forming temperature. When the heating temperature is 25 ° C. or higher and 45 ° C. or lower, it can be suitably used for a shrink film.

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

(Production Example 1 of Color Material Dispersion)
<Preparation of black pigment dispersion>
Carbon black (trade name: Black Pearls (registered trademark) 1000, manufactured by Cabot Corporation, BET specific surface area: 343 m ² / g, dibutyl phthalate absorption (DBPA): 105 mL / 100 g) 100 g, 2.5 N (normative) Carbon black pigment added to 3,000 mL of sodium hypochlorite solution, stirred at a temperature of 60 ° C. and a speed of 300 rpm, reacted for 10 hours and oxidized to give a carboxylic acid group on the surface of carbon black A reaction solution containing was obtained. This reaction solution was filtered, and the carbon black pigment separated by filtration was neutralized with a sodium hydroxide solution and ultrafiltered to obtain a pigment dispersion. Next, ultrafiltration using a dialysis membrane is performed using the pigment dispersion and ion-exchanged water, and then ultrasonic dispersion is performed using an ultrasonic dispersion device (device name: UH-600S, manufactured by SMT Co., Ltd.). A black pigment dispersion having a pigment solid content of 20% by mass was obtained.

(Production Example 2 of Color Material Dispersion)
<Preparation of cyan pigment dispersion>
Except for changing the carbon black to Pigment Blue 15: 4 (trade name: SMART Cyan 3154BA, manufactured by SENSIENT) in Preparation Example 1 of the colorant dispersion, the same as in Preparation Example 1 of the colorant dispersion, A cyan pigment dispersion having a pigment solid content of 20% by mass was obtained.

(Production Example 3 of Color Material Dispersion)
<Preparation of magenta pigment dispersion>
A pigment is produced in the same manner as in Color Material Dispersion Example 1 except that the carbon black is changed to Pigment Red 122 (trade name: Pigment Red 122, manufactured by Sun Chemical Co.) in Preparation Example 1 of the color material dispersion. A magenta pigment dispersion having a solid content of 20% by mass was obtained.

(Production Example 4 of Color Material Dispersion)
<Preparation of yellow pigment dispersion>
Pigment solids were prepared in the same manner as in Color Material Dispersion Example 1, except that the carbon black was changed to Pigment Yellow 74 (trade name: SMART Yellow 3074BA, manufactured by SENSIENT). A yellow pigment dispersion having a content of 20% by mass was obtained.

(Synthesis Example 1 of Resin Emulsion)
<Synthesis of Polyester Urethane Resin Emulsion A Having Polyolefin Structure>
Polyester diol [1] having a polyolefin structure 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, 618 parts by mass, , 4-butanediol 19 parts by weight, dimethylolpropionic acid 102 parts by weight, isophorone diisocyanate (IPDI) 290 parts by weight, and acetone 670 parts by weight were reacted at 80 ° C. for 10 hours with stirring, and the NCO content was 0. An acetone solution of a polyester urethane resin having an NCO-terminated polyolefin structure of 20% by mass was obtained. The acetone solution was cooled to 30 ° C. and 42 parts by mass of 28% by mass ammonia water was added. Next, 1,515 parts by mass of water is added to the acetone solution, and acetone is removed under reduced pressure at 50 ° C. or more and 60 ° C. or less. The solid content concentration is 40.0% by mass and the viscosity at 25 ° C. is 660 mPa · s. A polyester urethane resin dispersion having a polyolefin structure was obtained. The number average molecular weight (hereinafter the same) measured by gel permeation chromatography (GPC) of the polyester urethane resin dispersion having a polyolefin structure was 15,000. The obtained polyester urethane resin dispersion having a polyolefin structure is subjected to a dispersion treatment with a paint conditioner (manufactured by Red Devil, adjustable in speed within a range of 50 rpm to 1,425 rpm), and a particle size analyzer (device name: Microtrack) A polyester urethane resin emulsion A having a polyolefin structure with a volume average particle size of 32 nm was obtained by measurement with MODEL UPA 9340 (manufactured by Nikkiso Co., Ltd.).

(Synthesis Example 2 of Resin Emulsion)
<Synthesis of Polyester Urethane Emulsion B Having Polyolefin Structure>
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 of 3,600, and a weight average molecular weight / number. 166.91 parts by mass of an ethylene-propylene copolymer having an average molecular weight (Mw / Mn) of 1.65 was charged, and nitrogen substitution was performed. Then, after raising the temperature to 160 ° C., 490.60 parts by mass of 2-hydroxybutyl acrylate (trade name: Light acrylate HOB-A, manufactured by Kyoeisha Chemical Co., Ltd.) weighed in the dropping funnel at the same temperature, and 10.71 parts by mass of di (tert-butyl) peroxide (manufactured by Katayama Chemical Co., Ltd.) was added dropwise over 2 hours.
After dropping, the reaction was performed at 160 ° C. for 2 hours, and then the temperature was raised to 170 ° C., and a reduced pressure treatment was performed at 170 ° C. for 3 hours under the condition of 1.33 kPa or less to obtain polyol A having a polyolefin structure. Obtained.

  Next, in a reaction vessel into which a stirrer, a reflux condenser, and a thermometer are inserted, 1,500 parts by mass of polyester polyol (trade name: Polylite OD-X-2420, manufactured by DIC Corporation), 200 parts by mass of polyolefin-modified polyol. 2,2-dimethylolpropionic acid (DMPA) 220 parts by mass and N-methylpyrrolidone (NMP) 1,347 parts by mass were charged in a nitrogen stream and heated to 60 ° C. to dissolve DMPA. Next, 1,445 parts by weight of 4,4′-dicyclohexylmethane diisocyanate and 2.6 parts by weight of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out the urethanization reaction over 5 hours. A prepolymer was obtained. The reaction mixture was cooled to 80 ° C., 149 parts by mass of triethylamine was added thereto, and 4,340 parts by mass were extracted from the mixture, and 5,400 parts by mass of water and 15 parts by mass of triethylamine were obtained with vigorous stirring. It was added into the mixed solution. Next, 1,500 parts by mass of ice is added, and 626 parts by mass of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution is added to perform a chain extension reaction so that the solid content concentration becomes 40% by mass. The solvent was distilled off, and dispersion treatment was performed in the same manner as in Resin Emulsion Synthesis Example 1 to obtain a polyester urethane resin emulsion B having a polyolefin structure with a volume average particle diameter of 121 nm.

(Synthesis Example 3 of Resin Emulsion)
<Synthesis of polyether urethane resin emulsion having polyolefin structure>
In Synthesis Example 2 of the resin emulsion, the polyester polyol (trade name: Polylite OD-X-2420, manufactured by DIC Corporation) is changed to the polyether polyol (trade name: Hiflex D2000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Except for the above, a polyetherurethane resin emulsion having a polyolefin structure in which the volume average particle size of the resin emulsion is 58 nm and the solid content concentration is 40% by mass was obtained in the same manner as in Resin Emulsion Synthesis Example 2.

(Synthesis Example 4 of Resin Emulsion)
<Synthesis of polyester urethane resin emulsion>
The volume average particle size is 44 nm and solids in the same manner as in the resin emulsion synthesis example 2 except that no polyol A having a polyolefin structure was used in the prepolymer formation reaction of the resin emulsion synthesis example 2. A polyester-based urethane resin emulsion having a partial concentration of 40% by mass was obtained.

(Resin Emulsion Synthesis Example 5)
<Synthesis of polyolefin resin emulsion>
Propylene-based random copolymer (mass ratio (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., and thermal degradation is performed. A propylene random copolymer was obtained. After 100 parts by weight of the above-mentioned degraded propylene random copolymer, 4 parts by weight of methyl methacrylate, 4 parts by weight of ethylhexyl acrylate, and 3 parts by weight of dicumyl peroxide are sufficiently mixed in advance, they are supplied to a twin screw extruder. , Residence time 5 minutes, rotation speed 300 rpm, barrel temperature 120 ° C. (first barrel, second barrel), 180 ° C. (third barrel, fourth barrel), 100 ° C. (fifth barrel), and 130 ° C. Reaction was carried out under the conditions of (sixth barrel to eighth barrel) to obtain an acrylate-polyolefin copolymer.

  In a 2 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 200 parts by mass of the resulting acrylate-polyolefin copolymer, polyoxyethylene alkylamine (surfactant) 35 parts by mass, 8 parts by mass of stearyl glycidyl ether and 36 parts by mass of toluene were added and kneaded at 120 ° C. for 30 minutes. Thereafter, 8 parts by mass of 2-amino-2-methyl-1-propanol was added over 5 minutes, held for 5 minutes after the addition, and then 970 parts by mass of high purity water heated to 90 ° C. were added over 40 minutes. After distilling off toluene by vacuum treatment, the mixture was gradually cooled to room temperature with stirring, the water content was adjusted so that the solid content concentration was 40% by mass, and the volume was adjusted in the same manner as in Synthesis Example 1 of the resin emulsion. A polyolefin resin emulsion having an average particle size of 140 nm was obtained.

(Synthesis Example 6 of Resin Emulsion)
<Synthesis of acrylic resin emulsion>
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 parts by mass of ion-exchanged water and 1 part by mass of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. Maintaining the internal temperature at 70 ° C., adding 4 parts by mass of potassium persulfate as a polymerization initiator, and after dissolution, 450 parts by mass of ion-exchanged water, 3 parts by mass of sodium lauryl sulfate, 20 parts by mass of acrylamide, 365 parts by mass of styrene, An emulsion prepared by adding 545 parts by mass of butyl acrylate and 10 parts by mass of methacrylic acid with stirring was continuously added dropwise to the reaction solution over 4 hours. After completion of the dropwise addition, aging was performed for 3 hours to obtain an aqueous liquid. After cooling the obtained aqueous liquid to normal temperature, ion exchange water and sodium hydroxide aqueous solution were added, and solid content concentration was adjusted to 30 mass% and pH8. The mixture was stirred and dispersed in the same manner as in Synthesis Example 1 of the resin emulsion to obtain an acrylic resin emulsion having a volume average particle size of 100 nm.

Example 1
Black pigment dispersion 20% by mass, Polyester urethane resin emulsion A having a polyolefin structure 15% by mass, 1-methoxy-2-propanol (manufactured by Daicel Corporation) 5% by mass, 1,2-propanediol (manufactured by ADEKA Corporation) After mixing and stirring 20% by mass, fluorine surfactant (trade name: FS-300, manufactured by DuPont) 2% by mass, Proxel LV (Avicia) 0.1% by mass, and the remaining amount of ion-exchanged water Then, the ink was filtered through a polypropylene filter (Nippon Pole Co., Ltd.) having an average pore diameter of 0.2 μm to prepare ink 1. Table 1 shows the composition.

(Examples 2 to 19 and Comparative Examples 1 to 7)
Inks 2 to 26 were produced in the same manner as in Example 1, except that the compositions and contents described in Tables 1 to 4 were changed.

In addition, in the said Tables 1-4, the brand name of a component and the manufacturer name are as follows.
・ 1,2-butanediol: manufactured by Shinko Organic Chemical Co., Ltd. ・ diethylene glycol monobutyl ether: manufactured by KH Neochem Co., Ltd. ・ 3-methyl-3-methoxy-1-butanol: manufactured by Kuraray Co., Ltd. ・ Fluorine-based surfactant: Product name: FS-300, manufactured by DuPont

  About the produced Examples 1-19 and the ink 1-26 of Comparative Examples 1-7, "adhesion" to various base materials, such as a non-permeable base material, was evaluated as follows. The results are shown in Table 5.

<Adhesion>
Inks 1 to 26 of Examples 1 to 19 and Comparative Examples 1 to 7 were filled into an ink jet printer (device name: IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), and a polypropylene film (PP film) as the non-permeable substrate , Trade name: Pyrene P2102, manufactured by Toyobo Co., Ltd., polyethylene terephthalate film (PET film, trade name: Espet E5100, manufactured by Toyobo Co., Ltd.), and nylon film (ONY film, trade name: Harden N1100, Toyobo Co., Ltd.) The solid image having an ink adhesion amount of 1.0 mg / cm ² was recorded on the product and dried at room temperature (25 ° C.) overnight or at 40 ° C. for 1 hour. With respect to the solid part of the obtained solid image, the number of remaining squares of 100 test squares is counted by a cross-cut peel test using a cloth adhesive tape (trade name: 123LW-50, manufactured by Nichiban Co., Ltd.) Based on the following evaluation criteria, “adhesion” to the substrate was evaluated. In the above evaluation, the allowable range is “C” or more for drying at room temperature overnight, and “B” or more for drying at 40 ° C. for 1 hour.
-Evaluation criteria-
A: The number of remaining cells was 100 B: The number of remaining cells was 95 or more and 99 or less C: The number of remaining cells was 80 or more and 94 or less D: The number of remaining cells was 79 or less

Examples 1 to 8 are particularly preferable examples of the present invention, and are not affected by ink color types and other organic solvents, and are not only dried at 40 ° C. for 1 hour but also dried at room temperature (25 ° C.) overnight. It can also be seen that sufficient adhesion to the substrate can be secured.
In Examples 9 and 10, the content of 1-methoxy-2-propanol is less than 5% by mass, and the effect of improving the adhesion to various substrates is small, so compared with Examples 1-8. Although the adhesion is somewhat inferior, it can be seen that sufficient adhesion to the substrate can be obtained by drying at 40 ° C. for 1 hour.
In Example 11, since the content of the polyester urethane resin emulsion B having a polyolefin structure is less than 2.0% by mass and the amount of the resin is small, the adhesion to the base material is inferior, but there is no problem in practical use. It can be seen that the sex can be secured.
In Example 13, the content of the polyester urethane resin having a polyolefin structure exceeds 9% by mass, and the amount of the resin is large compared to Example 12 in which the content is 9% by mass. It can be seen that the adhesion to the substrate slightly decreases.
Examples 14 to 19 are examples in which the content of the color material was changed, not affected by the content of the color material, and not only drying at 40 ° C. for 1 hour but also at room temperature (25 ° C.) overnight drying, It can be seen that sufficient adhesion to the substrate can be secured.
Comparative examples 1-5 are examples which contain resin other than the polyester urethane resin which has a polyolefin structure, or do not contain resin, and it turns out that it is difficult to make it adhere | attach on a wide base material with sufficient balance.
Comparative Examples 6 and 7 are examples that do not contain 1-methoxy-2-propanol, and it can be seen that the adhesion to the substrate is poor overall.

As an aspect of this invention, it is as follows, for example.
<1> An ink containing water, a coloring material, an organic solvent, and a resin,
The organic solvent contains 1-methoxy-2-propanol;
The ink includes a polyester urethane resin having a polyolefin structure.
<2> The ink according to <1>, wherein the content of 1-methoxy-2-propanol is 5% by mass or more.
<3> The ink according to any one of <1> to <2>, wherein a content of the polyester urethane resin having the polyolefin structure is 2.0% by mass or more and 9% by mass or less.
<4> The ink according to any one of <1> to <3>, wherein the color material is a pigment.
<5> The ink according to any one of <1> to <4>, further including a surfactant.
<6> The ink according to <5>, wherein the surfactant is a fluorine surfactant.
<7> The ink according to any one of <1> to <6>, which is for inkjet.
<8> The ink according to any one of <1> to <7>, wherein the content of the coloring material is 0.1% by mass or more and 15% by mass or less.
<9> The ink according to any one of <1> to <8>, wherein the boiling point of the organic solvent is 250 ° C. or less.
<10> The above <1>, wherein the organic solvent further contains at least one of 1,2-propanediol, 1,2-butanediol, diethylene glycol monobutyl ether, and 3-methyl-3-methoxy-1-butanol. To <9>.
<11> The ink according to any one of <1> to <10>, wherein the content of the organic solvent is 1% by mass or more and 60% by mass or less.
<12> The ink according to any one of <1> to <11>, wherein a volume average particle diameter of the polyester urethane resin having the polyolefin structure is 10 nm or more and 1,000 nm or less.
<13> The ink according to any one of <1> to <12>, wherein the polyester urethane resin having the polyolefin structure has a volume average particle diameter of 10 nm to 200 nm.
<14> The ink according to any one of <1> to <13>, wherein a volume average particle diameter of the polyester urethane resin having a polyolefin structure is 10 nm or more and 50 nm or less.
<15> The ink according to any one of <1> to <14>, wherein the water content is 10% by mass or more and 90% by mass or less.
<16> An ink cartridge comprising the container according to any one of <1> to <15>.
<17> Inkjet recording comprising an ink flying step of applying an stimulus to the ink according to any one of <1> to <15> and causing the ink to fly to record an image on a recording medium. Is the method.
<18> The inkjet recording method according to <17>, further including a heating step after the ink flying step.
<19> The inkjet recording method according to <18>, wherein the heating temperature in the heating step is 35 ° C. or higher and 45 ° C. or lower.
<20> An ink jet recording apparatus comprising an ink applying unit that applies a stimulus to the ink according to any one of <1> to <15> and applies the ink to a recording medium.
<21> A recorded matter comprising an image recorded with the ink according to any one of <1> to <15>.

  The ink according to any one of <1> to <15>, the ink cartridge according to <16>, the ink jet recording method according to <17> to <19>, and the ink jet recording according to <20>. The apparatus and the recorded matter described in <21> can solve the conventional problems and achieve the object of the present invention.

JP 2010-116459 A

Claims (10)

An ink containing water, a coloring material, an organic solvent, and a resin,
The organic solvent contains 1-methoxy-2-propanol;
An ink characterized in that the resin contains a polyester urethane resin having a polyolefin structure.   The ink according to claim 1, wherein the content of 1-methoxy-2-propanol is 5% by mass or more.   The ink according to any one of claims 1 to 2, wherein a content of the polyester urethane resin having a polyolefin structure is 2.0% by mass or more and 9% by mass or less.   The ink according to claim 1, wherein the color material is a pigment.   The ink according to claim 1, further comprising a surfactant.   The ink according to claim 5, wherein the surfactant is a fluorine surfactant.   The ink according to any one of claims 1 to 6, which is used for inkjet.   An ink jet recording method comprising: an ink flying step of recording an image on a recording medium by applying a stimulus to the ink according to claim 1 and causing the ink to fly.   The ink jet recording method according to claim 8, further comprising a heating step after the ink flying step.   The inkjet recording method according to claim 9, wherein a heating temperature in the heating step is 35 ° C. or higher and 45 ° C. or lower.