JP2017210528A - Ink set, inkjet recording method, inkjet recording device and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink set excellent in scratch resistance of an obtained image and adhesion to a non-permeable recording medium such as a plastic film.SOLUTION: An ink set includes a white ink and a non-white ink. The white ink includes water, an organic solvent, a coloring material, and at least one kind selected from a polyurethane resin particle, an acrylic urethane resin particle, a polyolefin resin particle, a polyester resin particle and a polyolefin modified polyester urethane resin particle. The non-white ink includes water, an organic solvent and a polyurethane resin particle.SELECTED DRAWING: None

Description

  The present invention relates to an ink set, an ink jet recording method, an ink jet recording apparatus, and a recorded matter.

  In order to improve durability such as light resistance, water resistance, and wear resistance in industrial applications such as advertising and signboards and packaging materials such as food, beverages and daily necessities, for example, non-permeable recording media such as plastic films are used. Various inks used for the non-permeable recording medium have been developed.

  As such an ink, for example, a solvent-based ink using an organic solvent as a solvent, an ultraviolet curable ink mainly containing a polymerizable monomer, and the like are widely used. However, there is a concern that the solvent-based ink may affect the environment due to evaporation of the organic solvent. The UV curable ink may have a limited choice of polymerizable monomers used from the viewpoint of safety.

  In view of this, an ink set that has a low environmental load and can be directly recorded on an impermeable recording medium has been proposed (see, for example, Patent Documents 1 and 2).

  An object of the present invention is to provide an ink set having excellent scratch resistance of an image obtained and excellent adhesion to a non-permeable recording medium such as a plastic film.

  The ink set of the present invention as means for solving the problems is an ink set having a white ink and a non-white ink, wherein the white ink is water, an organic solvent, a color material, Polyurethane resin particles, and at least one selected from acrylic urethane resin particles, polyolefin resin particles, polyester resin particles, and polyolefin-modified polyester urethane resin particles, wherein the non-white ink is water, an organic solvent, and polyurethane Contains resin particles.

  According to the present invention, it is possible to provide an ink set excellent in scratch resistance of an image to be obtained and adhesion to a non-permeable recording medium such as a plastic film.

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.

(Ink set)
The ink set of the present invention is an ink set having a white ink and a non-white ink, wherein the white ink is water, an organic solvent, a color material, polyurethane resin particles, acrylic urethane resin particles, At least one selected from polyolefin resin particles, polyester resin particles, and polyolefin-modified polyester urethane resin particles, and the non-white ink contains water, an organic solvent, and polyurethane resin particles, and further if necessary. Contains other ingredients.
In the ink set of the present invention, in the conventional ink set, the non-permeable recording medium such as the plastic film is often a transparent film, and white ink is used from the viewpoint of increasing the image density of the obtained image. In some cases, recording with a non-white ink is performed after the transparent film is concealed. In such a case, it is based on the finding that the scratch resistance of the recorded matter is reduced. Further, in the conventional ink set, the image is peeled off from the non-permeable recording medium against the friction and the background portion of the non-permeable recording medium is exposed, or the background portion of the non-permeable recording medium is in close contact. However, this is based on the knowledge that the color of the image may change due to part of the surface of the image being peeled off.

<White ink>
The white ink contains water, an organic solvent, a coloring material, and resin particles, and further contains other components as necessary.
The white ink is preferably recorded as a base on a non-permeable recording medium.

<< Resin particles >>
The resin particles include polyurethane resin particles and resin particles other than polyurethane resin particles (other resin particles).

<<< Polyurethane resin particles >>>
When the white ink contains the polyurethane resin particles, the ink coating itself becomes tough, breaks inside the ink coating, and a part of the ink coating is peeled off, or the surface of the ink coating It can suppress that a state changes and the color in a friction part changes.
Moreover, since it is contained in all colors, the adhesiveness of the coating films of each color can be improved, and it can prevent that a coating film peels in the boundary of each color.

  There is no restriction | limiting in particular as a glass transition temperature of the said polyurethane resin particle, Although it can select suitably according to the objective, 0 degrees C or less is preferable. When the glass transition temperature is 0 ° C. or lower, the ink coating film can be prevented from peeling off.

  Examples of the polyurethane resin particles include polyether-based urethane resin particles, polycarbonate-based urethane resin particles, and polyester-based urethane resin particles. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said polyurethane resin particle, According to the objective, it can select suitably, For example, the polyurethane resin particle etc. which are obtained by making a polyol and polyisocyanate react are mentioned.

-Polyol-
Examples of the polyol include polyether polyol, polycarbonate polyol, and polyester polyol. These may be used individually by 1 type and may use 2 or more types together.

--Polyether polyol--
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.

  Examples of the compound having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Diol, glycerin, trimethylolethane, trimethylolpropane and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used individually by 1 type and may use 2 or more types together.

  The polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of obtaining a binder for ink that can impart very excellent scratch resistance, polyoxytetramethylene glycol, polyoxy Propylene glycol is preferred. These may be used individually by 1 type and may use 2 or more types together.

--Polycarbonate polyol--
Examples of the polycarbonate polyol that can be used for the production of the polyurethane resin particles include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , Bisphenol-A, bisphe Relatively low molecular weight dihydroxy compounds such as polyol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate, poly Examples thereof include polyester polyols such as caprolactone. These may be used individually by 1 type and may use 2 or more types together.

--Polyester polyol--
Examples of the polyester polyol include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and copolymers thereof. Examples include polyester. These may be used individually by 1 type and may use 2 or more types together.

Examples of the low 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, anhydrides or ester-forming derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.

-Polyisocyanate-
Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used individually by 1 type and may use 2 or more types together. Among these, since the ink set of the present invention is also used for outdoor applications such as posters and signboards, it requires a coating film with extremely high long-term weather resistance. From the viewpoint of the long-term weather resistance, Cyclic diisocyanates are preferred.

Furthermore, the use of at least one alicyclic diisocyanate makes it easy to obtain the desired coating strength and scratch resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
As content of the said alicyclic diisocyanate, 60 mass% or more is preferable with respect to the isocyanate compound whole quantity.

[Production method of polyurethane resin particles]
The polyurethane resin particles can be obtained by a conventionally 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, the polyol and the polyisocyanate are reacted at an equivalent ratio in which an isocyanate group becomes excessive to produce an isocyanate-terminated urethane prepolymer.
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with a neutralizing agent as necessary, and then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. Can be obtained.

  Examples of the organic solvent that can be used in the production of the polyurethane resin particles include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; Examples include amides such as formamide, N-methylpyrrolidone, and N-ethylpyrrolidone. These may be used individually by 1 type and may use 2 or more types together.

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, adipic acid dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide.

  Examples of the other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Kind; water etc. are mentioned. These may be used alone or in combination of two or more as long as the storage stability of the ink is not lowered.

  The polyurethane resin particles are preferably polycarbonate polyurethane resin particles from the viewpoint of water resistance, heat resistance, abrasion resistance, weather resistance, and image scratch resistance due to the high cohesive strength of carbonate groups. In the case of the polycarbonate-based polyurethane resin particles, an ink suitable for a recorded material used in a harsh environment such as an outdoor use can be obtained.

  Commercially available products may be used as the polyurethane resin particles. For example, U-coat UX-485 (polycarbonate-based polyurethane resin particles), U-coat UWS-145 (polyester-based polyurethane resin particles), and Permarin UA-368T (polycarbonate-based polyurethane). Resin particles), Permarin UA-200 (polyether polyurethane resin particles) (manufactured by Sanyo Chemical Industries, Ltd.), and the like. These may be used individually by 1 type and may use 2 or more types together.

<<< Resin particles other than polyurethane resin particles (other resin particles) >>>
The other resin particles are at least one selected from acrylic urethane resin particles, polyolefin resin particles, polyester resin particles, and polyolefin-modified polyester urethane resin particles.
By including the other resin particles, the white ink can further improve adhesion to a non-permeable recording medium such as a plastic film.
This is because when white ink is dried on a recording medium and formed into a film together in close physical proximity with resin particles, it contains a similar structure and interacts with each other to form a uniform film. To be inspired.

-Acrylic urethane resin particles-
By containing the acrylic urethane resin particles, the white ink can improve the adhesion to the non-permeable recording medium, and in particular, can obtain extremely high adhesion to the acrylic resin film.

  The acrylic urethane resin particles may be formed by reacting an acrylic polymer having a terminal hydroxyl group with a urethane chain having an isocyanate group at the end, as long as urethane and acrylic are chemically bonded. Examples include coalescence. There is no restriction | limiting in particular as said polymer, According to the objective, it can select suitably, A graft type or a block type may be sufficient. Moreover, a core shell type | mold which has a core part containing an acrylic resin and a shell part containing the urethane resin formed in the said core part surface may be sufficient.

  The core-shell type in which the acrylic urethane resin particles have a core part made of an acrylic resin and a shell part made of a urethane resin will be described.

  The core-shell type acrylic urethane resin particles are not particularly limited and can be appropriately selected according to the purpose. For example, the core-shell type acrylic urethane resin particles can be obtained by seed polymerization, multistage polymerization, power feed method, or the like.

The acrylic urethane resin particles are preferably used as a resin emulsion, and the resin emulsion may be obtained by any method.
The acrylic urethane resin emulsion can be obtained as follows (a) to (d).
(A) After reacting at least one organic diisocyanate (A) and at least one polycarbonate polyol (B), an acid diol is added to the poly (carbonate-urethane) prepolymer in which a carboxyl group is introduced. A polymer (A1) is obtained.
(B) An acrylic monomer (C) is added to the poly (carbonate-urethane) prepolymer (A1) to obtain a prepolymer / monomer mixture.
(C) A tertiary amine is added to the mixture to be dispersed in water, and then a radical initiator and a chain extender are added to obtain an aqueous dispersion.
(D) By heating the aqueous dispersion to polymerize the acrylic monomer, an acrylic urethane resin emulsion having (A1) as a shell component and (C) copolymer as a core can be obtained.
In the polymerization in (d), a vinyl monomer may be added separately as necessary.
There is no restriction | limiting in particular as said vinyl-type monomer, According to the objective, it can select suitably, For example, butadiene, styrene, substituted styrene, vinyl acetate, vinyl butyrate, vinyl chloride, vinylidene chloride etc. are mentioned.

  There is no restriction | limiting in particular as said organic diisocyanate (A), According to the objective, it can select suitably, For example, an aliphatic, an alicyclic, an aliphatic aromatic, an aromatic etc. are mentioned, As a specific example, For example, ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6 -Toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, 1,5-naphthylene diisocyanate and the like.

  There is no restriction | limiting in particular as said acid diol, According to the objective, it can select suitably, For example, 2, 2- dimethylol propionic acid etc. are mentioned.

There is no restriction | limiting in particular as said polycarbonate polyol (B), Although it can select suitably according to the objective, It is preferable that it is a product obtained by making diol and a carbonate compound react.
The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, , 6-propanediol, diethylene glycol and the like.
There is no restriction | limiting in particular as said carbonate compound, According to the objective, it can select suitably, For example, ethylene carbonate, diphenyl carbonate, phosgene etc. are mentioned.

  There is no restriction | limiting in particular as said acrylic monomer (C), According to the objective, it can select suitably, For example, acrylic acid, methacrylic acid ester, etc. are mentioned. Of these, lower (1 to 6 carbon atoms) alkyl esters of acrylic acid and methacrylic acid are preferred.

  The tertiary amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triethylamine and dimethylethanolamine. These may be used individually by 1 type and may use 2 or more types together.

The radical initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2,2′-azobis (2,4-dimethylpentanenitrile), 2,2′-azobis (2- And azo type compounds such as methylpropanenitrile).
There is no restriction | limiting in particular as said chain extender, According to the objective, it can select suitably, For example, ethylenediamine, diethylenetriamine, triethylenetetramine etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  As the core-shell type acrylic urethane resin particles, those appropriately synthesized may be used, or commercially available products may be used. Examples of the commercially available product include a resin emulsion dispersed in water such as Acryt WEM series (WEM-200U, WEM-3000) manufactured by Taisei Fine Chemical Co., Ltd.

-Polyolefin resin particles-
By containing the polyolefin resin particles, the white ink can improve the adhesion to the non-permeable recording medium, and in particular, can obtain extremely high adhesion to the polyethylene resin film.

The said polyolefin resin particle means the polymer which uses an olefin compound as a monomer component.
There is no restriction | limiting in particular as said olefin compound, According to the objective, it can select suitably, For example, ethylene, propylene, butene, etc. are mentioned. These may be used alone or in combination as a mixture.

  There is no restriction | limiting in particular as a polymerization catalyst at the time of making it copolymerize, According to the objective, it can select suitably, For example, a Ziegler Natta catalyst, a metallocene catalyst, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to use a metallocene catalyst from the viewpoint of easily obtaining a polymer having a narrow molecular weight distribution.

Moreover, you may make it copolymerize with monomers other than an olefin compound as needed.
Examples of monomers other than the olefin compound include (meth) acrylic acid esters. In the case of a copolymer with the (meth) acrylic acid ester, higher adhesion to the recording medium and gloss can be obtained.
This is because when white ink is dried on a recording medium and formed into a film in close physical proximity to the acrylic resin particles, it contains a similar structure and interacts with each other to form a uniform film. This is because formation is encouraged.

The polyolefin resin particles are preferably added to the ink in a state dispersed in water.
The method for dispersing the polyolefin resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include known methods such as forced emulsification, phase inversion emulsification, D phase emulsification, and gel emulsification. The method etc. are mentioned.
However, when used for inkjet, the average particle diameter of the polyolefin resin particles is preferably 300 nm or less from the viewpoint of avoiding nozzle clogging. For this purpose, it is preferable to use a phase inversion emulsification method.

-Polyester resin particles-
By containing the polyester resin particles, the white ink can improve adhesion to the non-permeable recording medium, and in particular, can obtain extremely high adhesion to the polyester resin film.

  The weight average molecular weight of the polyester resin particles is preferably 30,000 or less from the viewpoint of easy control of the dispersed particle diameter. The weight average molecular weight can be measured using, for example, gel permeation chromatography (GPC).

  As a glass transition temperature (Tg) of the said polyester resin particle, 70 degrees C or less is preferable. When the glass transition temperature is 70 ° C. or lower, the breaking elongation (breaking elongation) can be increased, and the scratch resistance can be improved. In addition, when recording on a recording medium such as an exclusive inkjet paper having a coating layer such as glossy paper, it becomes easy to adhere to the recording medium.

  Commercially available products can be used as the polyester resin particles having a glass transition temperature (Tg) of 70 ° C. or lower. Examples of the commercially available products include Vylonal series (manufactured by Toyobo Co., Ltd.).

-Polyolefin-modified polyester urethane resin particles-
By containing the polyolefin-modified polyester urethane resin particles, the white ink can improve the adhesion to the non-permeable recording medium, and in particular, can obtain extremely high adhesion to the polypropylene resin film.
The polyolefin-modified polyester urethane resin means a polyester urethane resin having a polyolefin skeleton in the main chain or side chain. The polyester urethane resin can be obtained, for example, by reacting polyester polyol and polyisocyanate.

  In addition to the polyester urethane resin particles, as the polyurethane resin particles, for example, there are polyether urethane resin particles and polycarbonate urethane resin particles. Adhesiveness with a recording medium can be obtained.

As the polyolefin-modified polyester urethane resin particles, those appropriately synthesized may be used, or commercially available products may be used.
Examples of the commercially available products include Superflex 210 (Daiichi Kogyo Seiyaku Co., Ltd.).

There is no restriction | limiting in particular as a synthesis method of the said polyolefin modified polyester urethane resin, According to the objective, it can select suitably, For example, the method of Unexamined-Japanese-Patent No. 10-72562 etc. are mentioned.
That is, an acid group of a polyurethane resin comprising a polyolefin-modified polyester polyol, 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. May be neutralized with ammonia and / or an organic amine and dispersed in an aqueous medium.
Hereinafter, each material will be described.

--Polyolefin-modified polyester polyol--
The polyolefin-modified polyester polyol means a polyolefin-modified polyester containing hydroxyl groups at both ends and / or side chains of the molecule.
The method for producing the polyolefin-modified polyester polyol is not particularly limited and may be appropriately selected depending on the purpose. For example, dehydration polycondensation or transesterification reaction between a compound that imparts an olefin group and a dicarboxylic acid is performed. And a method for obtaining a polyolefin-modified polyester having a terminal hydroxyl 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. 5 or more and 42 or less 1,2-alkanediol; glycerol monohexyl ether, glycerol monooctyl ether, glycerol mono-2-ethylhexyl ether, glycerol monodecyl ether, glycerol monododecyl ether, glycerol monooctadecyl ether, etc. 6 or more carbon atoms 43 or less glycerin monoalkyl ether; glycerin hexanoic acid monoester, glycerin octanoic acid monoester, glycerin-2-ethylhexanoic acid monoester, glycerin decanoic acid monoester, glycerin dodecanoic acid monoe Ether, and the number 7 or 44 or less glycerol fatty acid monoester 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.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids having 4 to 10 carbon atoms (for example, adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, etc.) or ester-forming derivatives thereof, aromatic Examples thereof include dicarboxylic acids (for example, 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-
Examples of the other polyester polyols include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, These copolyesters can be mentioned.

Examples of the low molecular weight polyol include ethylene glycol and propylene glycol.
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.

--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-dichlorohexene-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, aliphatic or alicyclic diisocyanates are preferable from the viewpoint of requiring a coating film having long-term weather resistance.

--A compound having an acidic group and at least two active hydrogen-containing groups in the molecule--
Examples of the compound having an acid group and at least two active hydrogen-containing groups in the molecule include glycolic acid, tartaric acid, 4,6-dihydroxyisophthalic acid, α, α-dimethylolpropionic acid, α, α- Hydroxy acids such as dimethylol butyric acid, α, α-dimethylol nonanoic acid, and carboxyl group-containing polycaprolactone diol obtained by addition polymerization of caprolactone monomers thereto, hydroxysulfonic acids such as 1,7-dihydroxynaphthalenesulfonic acid, And aminosulfonic acid such as 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; α, α-dimethylolpropionic acid, α, α-dimethylolbutyric acid, and carboxyl obtained by addition polymerization of these with caprolactone monomer Group-containing polycaprolactone diols are preferred.

There is no restriction | limiting in particular as a manufacturing method of the said polyolefin modified polyester urethane resin particle, According to the objective, it can select suitably, For example, the following method is mentioned.
First, in the absence of a solvent or in the presence of an organic solvent, the two polyols and the polyisocyanate are reacted at an equivalent ratio in which an isocyanate group becomes excessive to produce an isocyanate-terminated urethane prepolymer.

  In this case, the ratio of the other polyester polyol and polyolefin-modified polyester polyol is preferably such that the portion derived from the polyol in the prepolymer has a molecular weight ratio of 60:40 or more, more preferably 80:20 or more, particularly preferably 90:10 or more.

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

Examples of usable organic solvents include ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, acetates such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, dimethylformamide, and N-methyl. Examples include amides such as pyrrolidone and N-ethylpyrrolidone. These may be used individually by 1 type and may use 2 or more types together.
As the chain extender, the same chain extender in the method for producing the polyurethane resin particles can be used.

[Method for dispersing resin particles]
If necessary, the resin particles may contain a dispersant such as a surfactant. From the viewpoint of easily obtaining an ink having a better coating film performance, a so-called self-emulsifying resin emulsion is used. preferable.

  In that case, the self-emulsifying resin emulsion preferably contains an anionic group having an acid value 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. From the point to provide, it is more preferable to contain 5 mgKOH / g or more and 50 mgKOH / g or less of anionic group.

  Further, 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. In order to introduce these anionic groups into the resin, these anionic groups A monomer having the above may be used.

  Moreover, since the said white ink disperse | distributes the said resin particle in water, surfactant can be used as needed, for example, a nonionic surfactant, anionic surfactant, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a nonionic surfactant is preferable from the viewpoint of water resistance of the dispersed fat particles.

  The nonionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester , Polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkyl alkanolamide And polyalkylene glycol (meth) acrylate. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.

  The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkyl sulfate esters, polyoxyethylene alkyl ether sulfates, alkyl benzene sulfonates, and α-olefin sulfonic acids. Salt, methyl taurate, sulfosuccinate, ether sulfonate, ether carboxylate, fatty acid salt, naphthalenesulfonic acid formalin condensate, alkylamine salt, quaternary ammonium salt, alkylbetaine, alkylamine oxide, etc. . Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  As content of the said surfactant, 0.1 mass% or more and 30 mass% or less are preferable with respect to the resin particle whole quantity, and 5 mass% or more and 20 mass% or less are more preferable. When the content is 30% by mass or less, an excessive amount of emulsifier necessary for forming resin particles does not significantly reduce adhesion and water resistance, and when a dry film is formed. It is possible to prevent the plastic effect and bleeding phenomenon from being caused, and to suppress the occurrence of blocking.

Moreover, a basic substance can be added as needed for the purpose of neutralizing the acidic component in a resin particle, and making it disperse | distribute to water.
The basic substance is not particularly limited and may be appropriately selected depending on the intended purpose. Sodium hydroxide, potassium hydroxide, ammonia, methylamine, propylamine, hexylamine, octylamine, ethanolamine, propanolamine , Diethanolamine, N-methyldiethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, 2-amino-2-methyl-1-propanol, morpholine, etc. Is mentioned. Among these, ammonia, triethylamine, 2-amino-2-methyl-1-propanol, and morpholine are preferable.
The content of the basic substance can be arbitrarily prepared according to the amount of the acidic component of the resin particles.

The resin particles are preferably used as a resin emulsion, and the resin emulsion may be obtained by any method.
As the resin emulsion, if necessary, a water-soluble organic solvent, an antiseptic, a leveling agent, an antioxidant, a light stabilizer, an ultraviolet absorber and the like can be blended.

<Organic solvent>
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, A water-soluble organic solvent etc. are mentioned. Water-soluble means, for example, that 5 g or more is dissolved in 100 g of water at 25 ° C.

  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, 3-methoxy-3-methylbutanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, 6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Polyhydric alcohols, ethylene glycol monoethyl ether, ethylene Polyol alcohol alkyl ethers such as recall monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monophenyl ether, ethylene Polyhydric alcohol aryl ethers such as glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone Nitrogen-containing heterocyclic compounds such as formamide, N-methylformamide, N, N-dimethylformua Amides such as de, monoethanolamine, diethanolamine, amines such as triethylamine, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and the like ethylene carbonate. These may be used individually by 1 type and may use 2 or more types together.

  Moreover, there is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, It is preferable that 3-methoxy-3-methyl- 1-butanol is included. If the 3-methoxy-3-methyl-1-butanol is contained, the scratch resistance of the ink coating can be improved, although the reason is not clear.

  The content of the organic solvent is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, based on the total amount of white ink, from the viewpoints of ink drying properties and ejection reliability. preferable.

  The content of 3-methoxy-3-methyl-1-butanol is preferably 6% by mass or less and more preferably 5% by mass or less with respect to the total amount of white ink from the viewpoint of scratch resistance.

<Color material>
As the color material, a material having a whiteness measured in accordance with ISO-2469 (JIS-8148) of an image recorded using white ink containing the color material may be 70 or more.

There is no restriction | limiting in particular as said coloring material, According to the objective, it can select suitably, For example, dye, a pigment, etc. are mentioned.
Examples of the pigment include metal oxides.
Examples of the metal oxide include titanium oxide, iron oxide, tin oxide, zirconium oxide, and iron titanate (a composite oxide of iron and titanium). These may be used individually by 1 type and may use 2 or more types together.

The number average particle diameter of the pigment is not particularly limited and may be appropriately selected depending on the intended purpose, but the maximum frequency is preferably 20 nm or more and 150 nm or less in terms of the maximum number. When the number average particle size is 20 nm or more, dispersion operation and classification operation are facilitated, and when it is 150 nm or less, not only pigment dispersion stability as ink is improved, but also ejection stability is excellent. Image quality such as image density is also high, which is preferable.
The number average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

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 pigment. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.
The pigment dispersion is obtained by 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.

  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.

  The content of the pigment is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the ink. Particularly preferred. When the content is 0.1% by mass or more and 15% by mass or less, image density, fixability, and ejection stability can be improved.

<Water>
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.

  The content of the water is preferably 15% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 40% by mass or less with respect to the total amount of the white ink. When the content is 15% by mass or more, high viscosity can be prevented and ejection stability can be improved. When the content is 60% by mass or less, wettability to a non-permeable recording medium is preferable. Image quality can be improved.

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

<Surfactant>
As the surfactant, any of 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.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorosurfactant include perfluoroalkyl phosphate compounds, perfluoroalkylethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain.
Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and in particular, fluorine-based compounds represented by the general formulas (F-1) and (F-2) A surfactant is preferred.
Formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
Formula (F-2)
_{C n F 2n + 1- CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the general formula (F-2), Y is H, or CnF _{2n + 1} , n is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CnF _{2n + 1,} where n is 4 to 6. An integer, or CpH _{2p + 1} , p is an integer of 1-19. a is an integer of 4-14.
A commercial item may be used as said fluorosurfactant.
As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250 FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova) Manufactured), Unidyne DSN-403N (produced by Daikin Industries, Ltd.) and the like. Among these, good print quality, particularly color developability, penetrability to paper, wettability, and leveling are significantly improved. FS-3100, FS-34, FS-300 manufactured by Chemours, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd. Particularly preferred are Fox PF-151N and Unidyne DSN-403N manufactured by Daikin Industries, Ltd.

  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.

[Method for producing white ink]
As the method for producing the white ink, for example, the water, the organic solvent, the coloring material, the polyurethane resin particles, the other resin particles, and, if necessary, the additive are produced by stirring and mixing. can do. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like can be used.

<Non-white ink>
The non-white ink contains water, an organic solvent, and polyurethane resin particles, preferably contains a coloring material, and further contains other components as necessary.
Examples of the non-white ink include color ink, black ink (black ink), gray ink, clear ink, and metallic ink. These may be used individually by 1 type and may use 2 or more types together.
The clear ink means an ink that does not include a color material and mainly includes resin particles, an organic solvent, water, and the like.
Examples of the color ink include cyan ink, magenta ink, yellow ink, light cyan ink, light magenta ink, red ink, green ink, blue ink, orange ink, and violet ink.

<< Polyurethane resin particles >>
As the polyurethane resin particles, the same polyurethane resin particles as those in the white ink can be used.
The polyurethane resin particles in the non-white ink are preferably the same as the polyurethane resin particles in the white ink. When the polyurethane resin particles in the white ink and the polyurethane resin particles in the non-white ink are the same, the adhesion between the coating films of each color can be improved.

<< Organic solvent >>
As the organic solvent, the same organic solvent as in the white ink can be used.
The organic solvent in the non-white ink is preferably the same as the organic solvent in the white ink. When the organic solvent in the white ink and the organic solvent in the non-white ink are the same, the adhesion between the coating films of the respective colors can be improved.

<< Water >>
As the water, the same water as in white ink can be used.

<< Color material >>
The color material used for the non-white ink is not particularly limited as long as it exhibits a non-white color, and can be appropriately selected according to the purpose, and examples thereof include dyes and pigments. These may be used alone or in combination of two or more. Among these, a pigment is preferable.
Examples of the pigment include inorganic pigments and organic pigments.

  As the inorganic pigment, for example, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, it is manufactured by a known method such as a contact method, a furnace method, or a thermal method. And carbon black. These may be used individually by 1 type and may use 2 or more types together.

Examples of the organic pigment include azo pigments (for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments). , Quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (eg basic dye chelates, acidic dye chelates), nitro pigments, nitroso pigments, aniline black, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
In addition, use of hollow resin particles and inorganic hollow particles is also possible.
Of these pigments, those having good affinity with the solvent are preferably used.

  As the pigment, for black, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11) And organic pigments such as aniline black (CI Pigment Black 1). These may be used individually by 1 type and may use 2 or more types together.

  For color, for example, 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; 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, 185, 190, 193, 209, 219; 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 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; I. Acid Red 52, 80, 82, 249, 254, 289; I. Acid Blue 9, 45, 249; C.I. I. Acid Black 1, 2, 24, 94; C.I. I. Food black 1, 2; I. Direct yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173; I. Direct Red 1, 4, 9, 80, 81, 225, 227; I. Direct blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195; I. Reactive red 14, 32, 55, 79, 249; I. Reactive black 3, 4, 35 etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The color material used for the metallic ink is a fine powder obtained by finely pulverizing a simple metal, an alloy, or a metal compound, and more specifically, aluminum, silver, gold, nickel, chromium, tin, zinc, indium. Any one or more of single metals selected from titanium, silicone, copper, and platinum, or alloys obtained by combining these groups of metals, or oxides of these groups of single metals or alloys, It is obtained by pulverizing one or more of nitride, sulfide, or carbide.

As a method of dispersing the pigment in the ink, a method similar to the method of dispersing the pigment in the white ink in the ink can be used.
Further, the pigment can be made into a pigment dispersion in the same manner as the pigment in the white ink.

  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.

  The content of the pigment is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the ink. Particularly preferred. When the content is 0.1% by mass or more and 15% by mass or less, image density, fixability, and ejection stability can be improved.

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

<< Surfactant >>
As the surfactant, the same surfactant as that in the additive of the white ink can be used.

<<< antifoaming agent >>>
As the antifoaming agent, the same antifoaming agent in the additive of the white ink can be used.

<< antiseptic and antifungal agent >>
As the antiseptic / antifungal agent, the same antiseptic / antifungal agent in the additive of the white ink can be used.

<< rust preventive agent >>
As the rust preventive agent, the same rust preventive agent as the additive for the white ink can be used.

<< pH adjuster >>
As the pH adjuster, the same pH adjuster as that in the additive of the white ink can be used.

  The physical properties of the non-white ink are not particularly limited, and the viscosity, surface tension, pH, and the like can be appropriately selected according to the purpose, but the same as the viscosity, surface tension, and pH of the white ink. can do.

<Recording medium>
The recording medium is not particularly limited and can be appropriately selected depending on the purpose. For example, plain paper, glossy paper, special paper, cloth, and the like can be used, but an impermeable recording medium is used. Can also form a good image. Moreover, it is not restricted to what is used as a general recording medium, Construction materials, such as a wallpaper and a flooring, Cloths, such as clothing for T-shirts, textiles, leather, etc. can be used suitably. Furthermore, ceramics, glass, metal, or the like can be used by adjusting the configuration of the path for conveying the recording medium.
The non-permeable recording medium is a recording medium having a surface with low water permeability and absorbency, including a material that does not open to the outside even if there are many cavities inside, more quantitatively. In the Bristow method, the recording medium has a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 .
As the non-permeable recording medium, for example, a plastic film such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, an acrylic resin film, a polyester film, a polyethylene resin film, a polypropylene resin film, or a polycarbonate film is preferably used. can do.
Conventionally, the vinyl chloride resin film has been widely used, but in recent years, dechlorinated vinyl materials have come to be used from the environmental viewpoint, and PET film, acrylic resin film, polyester film, polyethylene resin film, polypropylene resin film. A transparent film such as is used.
The ink set of the present invention can obtain high adhesion particularly to an acrylic resin film, a polyester film, a polyethylene resin film, and a polypropylene resin film.

[Method for producing non-white ink]
The non-white ink can be produced, for example, by stirring and mixing the water, the organic solvent, the polyurethane resin particles, and, if necessary, the additive. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like can be used.

(Ink container)
The ink container contains each ink in the ink set of the present invention in the container.
The ink storage container is configured to store the ink in a container and further include 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 an aluminum laminate film, a resin film, etc. What has at least etc. is mentioned.

<Recording apparatus and recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier complex machine, and a three-dimensional modeling apparatus.
In the present invention, the recording apparatus and the recording method are an apparatus capable of ejecting ink, various treatment liquids, and the like to a recording medium, and a method of performing recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and the recording method may include a heating unit used in the heating step 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.

  In the recording apparatus and the recording method, the case where black (K), cyan (C), magenta (M), and yellow (Y) are used has been described, and the white ink and the non-white ink are included. When printing using an ink set, white ink may be used instead of black (K), cyan (C), magenta (M), or yellow (Y), or black (K), cyan. In addition to (C), magenta (M), and yellow (Y), white ink may be used.

  The ink in the ink set of the present invention is not limited to the ink jet recording method and can be widely used. In addition to inkjet recording methods, 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, micro gravure coating method, reverse roll coating method, 4 to 5 roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, spray coating method and the like.

The inkjet recording method of the present invention includes a white ink application step for applying the white ink to a non-permeable recording medium, and an image is formed by applying the non-white ink on the surface to which the white ink is applied. An image forming step, and further include other steps as necessary.
The ink jet recording apparatus of the present invention includes an ink storage unit that stores the white ink and the non-white ink, an ink jet recording head that applies a stimulus to the white ink and the non-white ink, and causes the ink to fly. And, if necessary, other means.

  As the ink jet recording head, a piezoelectric element is used as a pressure generating means for pressurizing the ink in the ink flow path, and the diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path, thereby A so-called piezo-type one that discharges (refer to Japanese Patent Laid-Open No. 2-51734), a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-59911). In other words, the diaphragm and the electrode forming the wall surface of the ink flow path are opposed to each other, and the diaphragm is deformed by an electrostatic force generated between the vibration plate and the electrode. Any case of an electrostatic type in which ink droplets are changed and discharged (see Japanese Patent Laid-Open No. 6-71882) is included.

  The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose. For example, heat (temperature), pressure, vibration, light Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  There is no particular limitation on the mode of the ink flying, and it varies depending on the type of the stimulus. A method of applying energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and ejecting and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles Is mentioned. When the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element is bent, and the pressure chamber For example, a method in which the volume is reduced and the ink is ejected and ejected as droplets from the nozzle holes of the recording head.

  The size of the ink droplets to be ejected is preferably 3 pL or more and 40 pL or less, for example, and the ejection jet speed is preferably 5 m / s or more and 20 m / s or less, and the drive frequency is 1 kHz or more is preferable, and the resolution is preferably 300 dpi or more.

<Other processes and other means>
Examples of the other steps include a stimulus generation step and a control step.
Examples of the other means include stimulus generation means and control means.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal conversion element such as a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

As an example of the embodiment, when white ink is applied to the entire surface of the recording medium, it is applied by a coating method other than the ink jet recording method, and when recording with a non-white ink, the ink jet recording method is used. Is possible.
As another embodiment, it is possible to use an ink jet recording method for recording using white ink and recording using non-white ink.

<Recorded material>
The recorded matter of the present invention has a non-permeable recording medium, and a white recording layer and a non-white recording layer on the non-permeable recording medium, and further includes other layers as necessary. .
The white recording layer includes an organic solvent, a coloring material, a urethane resin, and at least one selected from an acrylic urethane resin, a polyolefin resin, a polyester resin, and a polyolefin-modified polyester urethane resin, and further necessary. Other ingredients are included accordingly.
The non-white recording layer contains an organic solvent and a urethane resin, preferably contains a coloring material, and further contains other components as necessary.

As the organic solvent and the color material in the white ink, the same organic solvent and color material of the white ink in the ink set of the present invention can be used.
Examples of the urethane resin, acrylic urethane resin, polyolefin resin, polyester resin, and polyolefin-modified polyester urethane resin in the white ink include polyurethane resin particles, acrylic urethane resin particles, polyolefin resin particles, polyester of white ink in the ink set of the present invention. The same resin as the urethane resin, acrylic urethane resin, polyolefin resin, polyester resin, and polyolefin-modified polyester urethane resin used for the resin particles and polyolefin-modified polyester urethane resin particles can be used.
As the organic solvent and color material in the non-white ink, the same organic solvent and color material as those of the non-white ink in the ink set of the present invention can be used.
As the urethane resin in the non-white ink, the same urethane resin used for the polyurethane resin particles of the white ink in the ink set of the present invention can be used.

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

(Preparation Example 1 of Pigment Dispersion)
<Preparation of black pigment dispersion>
After premixing the following prescription mixture, it was circulated and dispersed for 7 hours using a disk-type bead mill (manufactured by Shinmaru Enterprises Co., Ltd., KDL type, media: zirconia balls with a diameter of 0.3 mm) to obtain a black pigment dispersion ( Pigment solid content concentration: 15% by mass).
Carbon black pigment (trade name: Monarch 800, manufactured by Cabot Corporation) 15 parts by mass Anionic surfactant (trade name: Pionein A-51-B, manufactured by Takemoto Yushi Co., Ltd.) 2 parts by mass Ion exchange water ... 83 parts by mass

(Preparation Example 2 of Pigment Dispersion)
<Preparation of cyan pigment dispersion>
In Preparation Example 1 of Pigment Dispersion, the same procedure as in Preparation Example 1 of Pigment Dispersion was performed except that the carbon black pigment was changed to Pigment Blue 15: 3 (trade name: LIONOL BLUE FG-7351, manufactured by Toyo Ink Co., Ltd.). Thus, a cyan pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 3 of Pigment Dispersion)
<Preparation of magenta pigment dispersion>
Magenta was prepared in the same manner as in Preparation 1 of pigment dispersion, except that the carbon black pigment was changed to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.). A pigment dispersion (pigment solid content concentration: 15% by mass) was obtained.

(Preparation Example 4 of Pigment Dispersion)
<Preparation of yellow pigment dispersion>
In the same manner as in Preparation 1 of pigment dispersion, except that the carbon black pigment was changed to Pigment Yellow 155 (trade name: SMART Yellow 3074BA, manufactured by SENSIENT) in Preparation Example 1 of Pigment Dispersion The product (pigment solid content concentration: 15 mass%) was obtained.

(Preparation Example 5 of Pigment Dispersion)
<Preparation of white pigment dispersion>
25 parts by mass of titanium oxide (trade name: STR-100W, manufactured by Sakai Chemical Industry Co., Ltd.), 5 parts by mass of a pigment dispersant (trade name: TEGO Dispers 651, manufactured by Evonik), and 70 parts by mass of water are mixed, and a bead mill (product) Name: Research Lab, manufactured by Shinmaru Enterprises Co., Ltd., dispersed zirconia beads having a diameter of 0.3 mm for 5 minutes at a filling rate of 60%, 8 m / s, and a white pigment dispersion (pigment solid content concentration: 15). Mass%).

(Preparation example 1 of polyurethane resin particles)
<Preparation of polyurethane resin emulsion 1>
In a 2 L reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser, 100 parts by mass of methyl ethyl ketone, polyester polyol (1) (iPA / AA = 6/4 (molar ratio) and EG / NPG = Polyester polyol obtained from 1/9 (molar ratio), number average molecular weight: 2,000, average number of functional groups: 2, iPA: isophthalic acid, AA: adipic acid, EG: ethylene glycol, and NPG: neopentyl glycol) 345 parts by mass and 9.92 parts by mass of 2,2-dimethylolpropionic acid (DMPA) were charged and mixed uniformly at 60 ° C.
Thereafter, 45.1 parts by mass of triethylene glycol diisocyanate (TEGDI) and 0.08 parts by mass of dioctyltin dilaurate (DOTDL) were charged and reacted at 72 ° C. for 3 hours to obtain a polyurethane solution.

The polyurethane solution was charged with 80 parts by mass of IPA, 220 parts by mass of MEK, 3.74 parts by mass of triethanolamine (TEA), and 596 parts by mass of water, and phase-inverted. Then, MEK and IPA were removed with a rotary evaporator. A polyurethane resin emulsion 1 was obtained.
The obtained aqueous emulsion was cooled to room temperature, and then ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the solid content concentration to 30% by mass and pH 8.
The glass transition point (Tg) of this polyurethane resin emulsion 1 measured using “Thermo plus EVO2” (manufactured by Rigaku) was 0 ° C.

(Preparation example 2 of polyurethane resin particles)
<Preparation of polyurethane resin emulsion 2>
Polycarbonate diol (reaction product of 3-methyl-1,5-pentanediol and diphenyl carbonate) (number average molecular weight (Mn): 1,200) 1 in a reaction vessel into which a stirrer, a reflux condenser and a thermometer were inserted. , 500 parts by mass, 2,2-dimethylolpropionic acid (DMPA) 220 parts by mass, and N-methylpyrrolidone (NMP) 1,347 parts by mass under a nitrogen stream and heated to 60 ° C. to dissolve DMPA. It was. 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 a urethanization reaction over 5 hours, and an isocyanate-terminated urethane. A prepolymer was obtained. The reaction mixture was cooled to 80 ° C., 149 parts by mass of triethylamine was added thereto, 4,340 parts by mass were extracted from the mixture, and 5400 parts by mass of water and 15 parts by mass of triethylamine were mixed with vigorous stirring. Added into the solution. Next, 1,500 parts by mass of ice was added, and 626 parts by mass of a 35% by mass aqueous 1,6-hexamethylenediamine solution was added to carry out a chain extension reaction, and the solvent was kept so that the solid content concentration would be 30% by mass. To obtain a polyurethane resin emulsion 2.
The glass transition point (Tg) of this polyurethane resin emulsion 2 measured using “Thermo plus EVO2” (manufactured by Rigaku) was 10 ° C.

(Black ink preparation example 1)
<Preparation of black ink 1>
Black pigment dispersion 20.0% by mass, polyurethane resin emulsion (solid content concentration: 30% by mass) 2 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0 3. mass%, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol monomethyl ether 0% by mass, as surfactant, trade name: FS-300 (fluorinated surfactant, manufactured by DuPont, solid content concentration: 40% by mass), 1.0% by mass, as preservative, trade name: Proxel LV (Avicia) A polypropylene filter having a mean pore size of 0.2 μm (trade name) is added by adding 0.1% by mass and high purity water so that the total amount becomes 100% by mass, followed by mixing and stirring. Betafine polypropylene pleated filter PPG series, by filtration with 3M Co.), to obtain a black ink 1.

(Black ink preparation examples 2 to 5)
<Preparation of black ink 2-5>
Black inks 2 to 5 were obtained in the same manner as in black ink preparation example 1 except that the composition in black ink preparation example 1 was changed to the composition shown in Table 1 below.

In Table 1, the trade names of the components and the names of the manufacturing companies are as follows.
-Fluorosurfactant: manufactured by DuPont, trade name: FS-300, solid content concentration: 40% by mass
-Antiseptic: Avicia Co., Ltd., trade name: Proxel LV

(Cyan ink preparation example 1)
<Preparation of cyan ink 1>
Cyan pigment dispersion 20.0% by mass, polyurethane resin emulsion (solid content concentration: 30% by mass) 2 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0 3. mass%, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol monomethyl ether 0% by mass, as surfactant, trade name: FS-300 (fluorinated surfactant, manufactured by DuPont, solid content concentration: 40% by mass), 1.0% by mass, as preservative, trade name: Proxel LV (Avicia) A polypropylene filter having a mean pore size of 0.2 μm (trade name: trade name) etafine polypropylene pleated filter PPG series, by filtration with 3M Co.), to obtain a cyan ink 1.

(Cyan ink preparation examples 2 to 5)
<Preparation of cyan inks 2-5>
Cyan inks 2 to 5 were obtained in the same manner as in cyan ink preparation example 1 except that the composition in cyan ink preparation example 1 was changed to the composition shown in Table 2 below.

  In Table 2, the trade names and manufacturing company names of the fluorosurfactant and Proxel LV are the same as in Table 1.

(Magenta ink preparation example 1)
<Preparation of magenta ink 1>
Magenta pigment dispersion 20.0% by mass, polyurethane resin emulsion (solid content concentration: 30% by mass) 2 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0 3. mass%, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol monomethyl ether 0% by mass, as surfactant, trade name: FS-300 (fluorinated surfactant, manufactured by DuPont, solid content concentration: 40% by mass), 1.0% by mass, as preservative, trade name: Proxel LV (Avicia) A polypropylene filter having a mean pore size of 0.2 μm (trade name) is added by adding 0.1% by mass and high purity water so that the total amount becomes 100% by mass, followed by mixing and stirring. Betafine polypropylene pleated filter PPG series, by filtration with 3M Co.), to obtain a magenta ink 1.

(Magenta ink preparation examples 2 to 5)
<Preparation of magenta ink 2-5>
Magenta inks 2 to 5 were obtained in the same manner as in magenta ink preparation example 1 except that the composition was changed to the composition shown in Table 3 below.

  In Table 3, the trade names and manufacturing company names of the fluorosurfactant and Proxel LV are the same as in Table 1.

(Yellow ink preparation example 1)
<Preparation of yellow ink 1>
Yellow pigment dispersion 20.0% by mass, polyurethane resin emulsion (solid content concentration: 30% by mass) 2 23.3% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0 3. mass%, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol monomethyl ether 0% by mass, as surfactant, trade name: FS-300 (fluorinated surfactant, manufactured by DuPont, solid content concentration: 40% by mass), 1.0% by mass, as preservative, trade name: Proxel LV (Avicia) A polypropylene filter having a mean pore size of 0.2 μm (trade name) is added by adding 0.1% by mass and high purity water so that the total amount becomes 100% by mass, followed by mixing and stirring. Betafine polypropylene pleated filter PPG series, by filtration with 3M Co.) to obtain Yellow Ink 1.

(Yellow ink preparation examples 2 to 5)
<Preparation of yellow ink 2-5>
Yellow inks 2 to 5 were obtained in the same manner as in yellow ink preparation example 1 except that the composition of yellow ink preparation example 1 was changed to the composition shown in Table 4 below.

  In Table 4, the trade names and manufacturing company names of the fluorosurfactant and Proxel LV are the same as in Table 1.

(White ink preparation example A1)
<Preparation of white ink A1>
White pigment dispersion 20.0% by mass, polyurethane resin emulsion (solid content concentration: 30% by mass) 2 11.6% by mass, acrylic urethane resin emulsion 1 (trade name: WEM-3000, manufactured by Taisei Fine Chemical Co., Ltd., urethane: (Acryl = 8: 2, solid content concentration: 33% by mass) 10.7% by mass, 1,2-propanediol 12.0% by mass, 1,3-propanediol 10.0% by mass, 1,2-butanediol 3.0 mass%, 2,3-butanediol 3.0 mass%, 2-methyl-2,4-pentanediol 3.0 mass%, dipropylene glycol monomethyl ether 4.0 mass%, as a surfactant, Product name: FS-300 (fluorine surfactant, manufactured by DuPont, solid content concentration: 40% by mass) 1.0% by mass, preservative as product name: proxy Cell LV (manufactured by Abyssia) 0.1% by mass and high purity water were added so that the total amount was 100% by mass, mixed and stirred, and a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine) White ink A1 was obtained by filtering with a polypropylene pleated filter PPG series (manufactured by 3M).

(White ink preparation examples A2 to A7)
<Preparation of white inks A2 to A7>
White inks A2 to A7 were obtained in the same manner as in the white ink preparation example A1, except that the white ink preparation example A1 was changed to the composition shown in Table 5 below.

In Table 5, the trade names of the components and the names of the manufacturing companies are as follows.
Acrylic urethane resin emulsion 1: manufactured by Taisei Fine Chemical Co., Ltd., trade name: WEM-3000, urethane / acrylic = 8/2, solid content concentration: 33% by mass, pH: 7.6
Acrylic urethane resin emulsion 2: manufactured by Taisei Fine Chemical Co., Ltd., trade name: WEM-200U, urethane / acrylic = 8/2, solid content concentration: 38 mass%, pH: 7
-The brand name of a fluorosurfactant and Proxel LV, and a manufacturing company name are the same as that of the said Table 1.

(Example A1)
Ink set A1 was obtained by combining white ink A1 as the white ink and black ink 1, cyan ink 1, magenta ink 1, and yellow ink 1 as the non-white ink.

(Examples A2 to A6 and Comparative Examples A1 to A3)
Ink sets A2 to A9 were obtained in the same manner as in Example A1, except that the ink combinations in Example A1 were changed to the ink combinations shown in Table 6 below.

  Using the obtained ink set, “adhesion” and “scratch resistance” to the acrylic resin film were evaluated as follows. The results are shown in Table 6 below.

[Create image (form)]
Filled in an inkjet printer (device name: IPSiO GXe5500 remodeling machine, manufactured by Ricoh Co., Ltd.) and impervious recording medium (acrylic resin film, trade name: transparent acrylic film SPC-0640, manufactured by Mimaki Engineering Co., Ltd.) An image was formed as follows.
The IPSiO GXe5500 remodeling machine is remodeled from the IPSiO GXe5500 machine so that a recording corresponding to a recording speed of 30 m ² / hr with a printing width of 150 cm can be reproduced in A4 size, and the hot plate is installed and recorded. It was modified so that later heating conditions (heating temperature, heating time) could be changed.

-Formation of white image-
A solid image was recorded on an acrylic resin film using white ink at an ink adhesion amount of 0.6 g / cm ² . After recording, the solid image was dried for 3 minutes on a hot plate (device name: NINOS ND-1, manufactured by ASONE Co., Ltd.) set at 80 ° C. to obtain a white image.

-Formation of non-white image-
A single color solid image of each non-white ink was formed on the white image, and dried for 3 minutes on a hot plate (device name: NINOS ND-1, manufactured by ASONE CORPORATION) set at 80 ° C. A cyan single-color solid image, a magenta single-color solid image, a yellow single-color solid image, and a black single-color solid image recorded on a white image were obtained.

(Adhesion)
Based on the cross-cut peel test using a cloth adhesive tape (trade name: 123LW-50, manufactured by Nichiban Co., Ltd.) for each color single-color solid image, the number of remaining squares of 100 test squares was counted and based on the following evaluation criteria. The “adhesion” to the recording medium was evaluated. It is desirable in practical use that the evaluation is B or more. In addition, in the single-color solid image of each color of the black single-color solid image, the cyan single-color solid image, the magenta single-color solid image, and the yellow single-color solid image, the result of the color with the worst result is described as the evaluation result.
〔Evaluation criteria〕
AA: The number of remaining cells is 98 or more A: The number of remaining cells is 90 or more and less than 98 B: The number of remaining cells is 70 or more and less than 90 C: The number of remaining cells is less than 70

(Abrasion resistance)
After drying, the recording part is rubbed 100 times with a cotton cloth (Kanakin No. 3) under a load of 400 g, the recording part is visually observed, and the “color” of the rubbed part and the non-rubbed part based on the following evaluation criteria. “Change in taste”, “exposed white ink layer” in the rubbed area, and “exposed recording medium” in the rubbed area were evaluated. The results were determined according to the following criteria. In addition, in the single-color solid image of each color of magenta, cyan, black, and yellow, the result of the color with the worst result was described as the evaluation result. Further, in the rank evaluation of the scratch resistance, ranks A to C are levels that are not problematic in actual use, and rank D is a level that is problematic in actual use.
[Evaluation criteria for color]
A: There is no change in color between the rubbed part and the non-rubbed part. B: When observed closely, the color is slightly changed between the rubbed part and the non-rubbed part. C: Although it is not noticeable, it is rubbed. The color changes between the rubbed part and the non-rubbed part. D: The color change is noticeable between the rubbed part and the non-rubbed part [Evaluation criteria for exposure of the white ink layer]
A: The white ink layer is not exposed at all. B: When observed closely, there are a few portions where the white ink layer is exposed. C: There is a portion where the white ink layer is exposed although it is not conspicuous. D: White ink layer exposure is conspicuous [Evaluation criteria for recording medium exposure]
A: The recording medium is not exposed at all. B: When observed closely, there are a few portions where the recording medium is exposed. C: There is a portion where the recording medium is exposed although it is not noticeable. D: White ink layer The exposure of

(Preparation example 1 of polyolefin resin particles)
<Preparation of polyolefin resin emulsion 1>
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. to perform thermal degradation, and the degraded propylene-based random copolymer Coalescence was obtained.
100 parts by weight of a degenerated 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 mixed in advance and then supplied to a twin-screw extruder and retained. 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 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, 35 surfactant (polyoxyethylene alkylamine) Part 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 the toluene was distilled off by the reduced pressure treatment, the mixture was gradually cooled to room temperature while stirring, and the water content was adjusted so that the solid content concentration was 40% by mass, whereby a polyolefin resin emulsion 1 was obtained.

(Preparation example 2 of polyolefin resin particles)
<Preparation of polyolefin resin emulsion 2>
A polyolefin resin was prepared in the same manner as in Preparation Example 1 of a polyolefin resin particle, except that a copolymerization reaction with an acrylate ester was not performed and a degenerated propylene random copolymer was used as it was in Preparation Example 1 of a polyolefin resin particle. An emulsion (solid content concentration: 38% by mass) 2 was obtained.

(White ink preparation example B1)
<Preparation of white ink B1>
In the white ink preparation example A1, except that acrylic urethane resin emulsion (solid content concentration: 33% by mass) 1 10.7% by mass was changed to polyolefin resin emulsion (solid content concentration: 40% by mass) 1 8.8% by mass. Produced white ink B1 in the same manner as in white ink preparation example A1.

(White ink preparation examples B2 to B6)
<Preparation of white inks B2 to B6>
White inks B2 to B6 were obtained in the same manner as in the white ink preparation example B1, except that the white ink preparation example B1 was changed to the composition shown in Table 7 below.

  In Table 7, the trade names and manufacturing company names of the fluorosurfactant and Proxel LV are the same as in Table 1.

(Example B1)
Ink set B1 was obtained by combining white ink B1 as the white ink and black ink 1, cyan ink 1, magenta ink 1, and yellow ink 1 as the non-white ink.

(Examples B2 to B6 and Comparative Examples B1 to B2)
Ink sets B2 to B8 were obtained in the same manner as in Example B1 except that the ink combinations in Example B1 were changed to the ink combinations shown in Table 8 below.

  Ink obtained in the same manner as in Example A1, except that the acrylic resin film of the impermeable recording medium was changed to a polyethylene resin film (trade name: PE-3M, manufactured by Framura Chemical Co., Ltd.) in Example A1. Using the sets B1 to B8, “adhesion” and “scratch resistance” were evaluated. The results are shown in Table 8 below.

(White ink preparation example C1)
<Preparation of white ink C1>
In Preparation Example A1 of the white ink, 10.7% by mass of acrylic urethane resin emulsion (solid content concentration: 33% by mass) 1 8.8% by mass of polyester resin emulsion 1 (trade name: MD-2000, manufactured by Toyobo Co., Ltd., A white ink C1 was obtained in the same manner as in the white ink preparation example A1, except that the solid content concentration was changed to 40% by mass.

(White ink preparation examples C2 to C6)
<Preparation of white inks C2 to C6>
White inks C2 to C6 were obtained in the same manner as in the white ink preparation example C1, except that the white ink preparation example C1 was changed to the composition shown in Table 9 below.

In Table 9, the trade names of the components and the names of the manufacturing companies are as follows.
-Polyethylene resin emulsion 1: manufactured by Toyobo Co., Ltd., trade name: MD-2000, solid content concentration: 40% by mass
Polyethylene resin emulsion 2: manufactured by Kyoyo Chemical Industry Co., Ltd., trade name: Pluscoat Z-221, solid content concentration: 20% by mass
-The brand name of a fluorosurfactant and Proxel LV, and a manufacturing company name are the same as that of the said Table 1.

(Example C1)
An ink set C1 was obtained by combining the white ink C1 as the white ink and the black ink 1, the cyan ink 1, the magenta ink 1, and the yellow ink 1 as the non-white ink.

(Examples C2-C6 and Comparative Examples C1-C2)
Ink sets C2 to C8 were obtained in the same manner as in Example C1, except that the ink combinations in Example C1 were changed to the ink combinations shown in Table 10 below.

  Ink set obtained in the same manner as in Example A1 except that in Example A1, the acrylic resin film of the non-permeable recording medium was changed to a polyester resin film (trade name: Lumirror type S10, manufactured by Toray Industries, Inc.) C1 to C8 were used to evaluate "adhesion" and "scratch resistance". The results are shown in Table 10 below.

(Preparation example 1 of polyolefin-modified polyester urethane resin particles)
<Preparation of polyolefin-modified polyester urethane resin emulsion 1>
A polyolefin-modified polyester urethane resin emulsion (solid content concentration: 40% by mass) 1 was obtained in the same manner as in the method described in Example 9 of JP-A-10-72562.

(Preparation example 2 of polyolefin-modified polyester urethane resin particles)
<Preparation of polyolefin-modified polyester urethane resin emulsion 2>
In a separable flask equipped with a stirrer, a dropping funnel with two pressure equalizing tubes, a thermometer, and a water-cooled condenser, the ethylene component content was 48 mol%, the number average molecular weight (Mn) was 3600, and the weight average molecular weight ( Mw) /16.91 parts by mass of an ethylene / propylene copolymer having a number average molecular weight (Mn) of 1.65 was charged, followed by nitrogen substitution. 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 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-modified polyol A.
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 a urethanization reaction over 5 hours, and an isocyanate-terminated urethane. A prepolymer was obtained. This reaction mixture was cooled to 80 ° C., and 340 parts by mass of triethylamine was added to and mixed with this, and 4,340 parts by mass was extracted and mixed with 5,400 parts by mass of water and 15 parts by mass of triethylamine with vigorous stirring. Added into the 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 30% by mass. The solvent was distilled off to obtain a polyolefin-modified polyester urethane resin emulsion 2.

(White ink preparation example D1)
<Preparation of white ink D1>
In Preparation Example A1 of the white ink, 10.7% by mass of acrylic urethane resin emulsion (solid content concentration: 33% by mass) 1 is changed to 18.8% by mass of polyolefin-modified polyester urethane resin emulsion (solid content concentration: 40% by mass). A white ink D1 was obtained in the same manner as in the white ink preparation example A1, except that the changes were made.

(White ink preparation examples D2 to D6)
<Preparation of white inks D2 to D6>
In white ink preparation example D1, white inks D2 to D6 were obtained in the same manner as white ink preparation example D1 except that the composition was changed to the composition shown in Table 11 below.

  In Table 11, the trade names and manufacturing company names of the fluorosurfactant and Proxel LV are the same as in Table 1.

(Example D1)
Ink set D1 was obtained by combining white ink D1 as the white ink and black ink 1, cyan ink 1, magenta ink 1, and yellow ink 1 as the non-white ink.

(Examples D2 to D6 and Comparative Examples D1 to D2)
Ink sets D2 to D8 were obtained in the same manner as in Example D1 except that the ink combinations in Example D1 were changed to the combinations shown in Table 12 below.

  Ink set D1 was obtained in the same manner as in Example A1, except that in Example A1, the acrylic resin film of the non-permeable recording medium was changed to a polypropylene resin film (trade name: Pyrene P2102, manufactured by Toyobo Co., Ltd.). Using ˜D8, “adhesion” and “scratch resistance” were evaluated. The results are shown in Table 12 below.

As an aspect of this invention, it is as follows, for example.
<1> An ink set having a white ink and a non-white ink,
The white ink is water, an organic solvent, a coloring material, polyurethane resin particles, at least one selected from acrylic urethane resin particles, polyolefin resin particles, polyester resin particles, and polyolefin-modified polyester urethane resin particles. Contains,
The non-white ink is an ink set comprising water, an organic solvent, and polyurethane resin particles.
<2> The ink set according to <1>, wherein the polyurethane resin particles in the white ink and the polyurethane resin particles in the non-white ink are the same.
<3> The ink set according to any one of <1> to <2>, wherein a glass transition temperature of the polyurethane resin particles in the white ink and the non-white ink is 0 ° C. or lower.
<4> The ink set according to any one of <1> to <3>, wherein the organic solvent in the white ink and the organic solvent in the non-white ink are the same.
<5> The ink set according to any one of <1> to <4>, wherein the organic solvent in the white ink and the non-white ink contains 3-methoxy-3-methyl-1-butanol.
<6> The ink set according to <5>, wherein the content of 3-methoxy-3-methyl-1-butanol is 5% by mass or less.
<7> The ink set according to any one of <1> to <6>, wherein the color material in the white ink is a metal oxide.
<8> The ink set according to <7>, wherein the metal oxide is titanium oxide.
<9> The ink set according to any one of <1> to <8>, wherein the content of the color material in the white ink is 1% by mass or more and 10% by mass or less with respect to the total amount of the white ink. .
<10> The ink set according to any one of <1> to <9>, wherein the white ink and the non-white ink have a viscosity at 25 ° C. of 5 mPa · s to 30 mPa · s.
<11> The ink set according to any one of <1> to <10>, wherein the non-white ink is at least one selected from black ink, cyan ink, magenta ink, and yellow ink.
<12> The ink set according to any one of <1> to <11>, wherein the white ink or the non-white ink further includes a surfactant.
<13> The ink set according to <12>, wherein the surfactant is a fluorine surfactant.
<14> The ink according to any one of <12> to <13>, wherein the content of the surfactant is 0.001% by mass or more and 5% by mass or less based on the total amount of the white ink or the non-white ink. Is a set.
<15> a non-permeable recording medium;
A recorded matter having a white recording layer and a non-white recording layer on the non-permeable recording medium,
The white recording layer contains an organic solvent, a color material, a urethane resin, at least one selected from an acrylic urethane resin, a polyolefin resin, a polyester resin, and a polyolefin-modified polyester urethane resin,
The non-white recording layer contains an organic solvent, a color material, and a urethane resin.
<16> The recorded matter according to <15>, wherein the non-permeable recording medium is at least one selected from an acrylic resin film, a polyester resin film, a polyethylene resin film, and a polypropylene resin film.
<17> A white ink application step of applying a white ink in the ink set according to any one of <1> to <14> to a non-permeable recording medium;
An image forming step of forming an image by applying the non-white ink in the ink set according to any one of <1> to <14> on the surface to which the white ink is applied, This is an ink jet recording method.
<18> The inkjet recording method according to <17>, wherein the impermeable recording medium is at least one selected from an acrylic resin film, a polyester resin film, a polyethylene resin film, and a polypropylene resin film.
<19> The inkjet recording method according to any one of <17> to <18>, wherein the stimulus is at least one of heat and pressure.
<20> an ink storage unit that stores the white ink and the non-white ink in the ink set according to any one of <1> to <14>;
An ink jet recording apparatus comprising: an ink jet recording head that applies a stimulus to the white ink and the non-white ink and causes the ink to fly.

  The ink set according to any one of <1> to <14>, the recorded matter according to any one of <15> to <16>, and the ink jet recording according to any one of <17> to <19>. The method and the inkjet recording apparatus according to <20> can solve the above-described problems and achieve the object of the present invention.

JP 2011-252169 A Japanese Patent No. 5770209

400 Image Forming Apparatus 411 Ink Storage Unit 434 Ejection Head (Inkjet Recording Head)

Claims (9)

An ink set having a white ink and a non-white ink,
The white ink is water, an organic solvent, a coloring material, polyurethane resin particles, at least one selected from acrylic urethane resin particles, polyolefin resin particles, polyester resin particles, and polyolefin-modified polyester urethane resin particles. Contains,
The ink set, wherein the non-white ink contains water, an organic solvent, and polyurethane resin particles.   The ink set according to claim 1, wherein the polyurethane resin particles in the white ink and the polyurethane resin particles in the non-white ink are the same.   The ink set according to claim 1, wherein a glass transition temperature of the polyurethane resin particles in the white ink and the non-white ink is 0 ° C. or less.   The ink set according to any one of claims 1 to 3, wherein the organic solvent in the white ink and the organic solvent in the non-white ink are the same.   The ink set according to any one of claims 1 to 4, wherein the organic solvent in the white ink and the non-white ink contains 3-methoxy-3-methyl-1-butanol.   The ink set according to claim 5, wherein a content of the 3-methoxy-3-methyl-1-butanol is 5% by mass or less. A non-permeable recording medium;
A recorded matter having a white recording layer and a non-white recording layer on the non-permeable recording medium,
The white recording layer contains an organic solvent, a color material, a urethane resin, at least one selected from an acrylic urethane resin, a polyolefin resin, a polyester resin, and a polyolefin-modified polyester urethane resin,
The recorded matter, wherein the non-white recording layer contains an organic solvent, a color material, and a urethane resin. A white ink application step for applying a white ink in the ink set according to any one of claims 1 to 6 to a non-permeable recording medium;
An ink jet recording comprising: an image forming step of forming an image by applying the non-white ink in the ink set according to any one of claims 1 to 6 on the surface to which the white ink is applied. Method. An ink storage portion for storing white ink and non-white ink in the ink set according to any one of claims 1 to 6;
An ink jet recording apparatus comprising: an ink jet recording head that applies a stimulus to the white ink and the non-white ink and causes the ink to fly.