JP2021063167A - Inkjet ink composition, production method of printed matter, and production method of transfer sheet - Google Patents

Abstract

To provide an inkjet ink composition as a new ink composition that can be used in print technology of an ink composition for a living body, and to provide a production method of a printed matter using the above inkjet ink composition and a production method of a transfer sheet.SOLUTION: An inkjet ink composition comprises an aqueous medium and a coloring material, in which the coloring material contains at least one kind selected from the group consisting of a cosmetic pigment and a cosmetic dye. The production method of a printed matter includes a step of printing with the above inkjet ink composition by an inkjet recording system to obtain a printed matter. A production method of a transfer sheet that can transfer a printed matter on a substrate to an adherend is provided, which includes a step of obtaining a printed matter on a substrate by the above production method of a printed matter.SELECTED DRAWING: None

Description

The present invention relates to an ink composition for inkjet, a method for producing a printed matter, and a method for producing a transfer sheet.

Face paints, body paints, and the like that print ink compositions on parts such as the face, limbs, and torso in a living body are known. For example, Patent Document 1 below discloses paints that can be used for face paint, body paint, and the like.

Japanese Unexamined Patent Publication No. 2003-277232

As described above, a new printing technique is required for a technique for printing an ink composition on a living body from the viewpoint of applying a wide variety of decorations.

The problem to be solved by the present invention is to provide an inkjet ink composition as a new ink composition that can be used in a printing technique for an ink composition for a living body, and further, the inkjet ink composition is used. The present invention provides a method for producing a printed matter and a method for producing a transfer sheet.

One aspect of the present invention provides an inkjet ink composition containing an aqueous medium and a coloring material, wherein the coloring material comprises at least one selected from the group consisting of cosmetic pigments and cosmetic dyes. ..

According to the inkjet ink composition according to one aspect of the present invention, it is possible to apply high-definition decoration to a living body by printing by an inkjet recording method, and by using a cosmetic pigment or a cosmetic dye. , High-definition decoration can be applied to the living body while suppressing adverse effects on the living body.

Another aspect of the present invention provides a method for producing a printed matter, which comprises a step of obtaining a printed matter by printing the above-mentioned ink composition for inkjet by an inkjet recording method.

Another aspect of the present invention is a method for producing a transfer sheet capable of transferring a printed matter on a substrate to an adherend, and a step of obtaining the printed matter on the substrate by the above-mentioned method for producing a printed matter. Provided is a method for producing a transfer sheet.

According to one aspect of the present invention, it is possible to provide an ink composition for inkjet as a new ink composition that can be used in a printing technique for an ink composition for a living body. According to another aspect of the present invention, it is possible to provide a method for producing a printed matter and a method for producing a transfer sheet using the ink composition for inkjet. According to the ink-jet ink composition according to one aspect of the present invention, high-definition decoration can be applied to a living body while suppressing adverse effects on the living body.

It is a schematic diagram of a microreactor.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, "(meth) acrylic acid" is a general term for acrylic acid and methacrylic acid corresponding thereto, and the same applies to other similar expressions such as "(meth) acrylate". ..

The inkjet ink composition (inkjet ink) according to the present embodiment contains an aqueous medium (A) and a coloring material (B), and the coloring material (B) comprises a cosmetic pigment and a cosmetic dye. Includes at least one cosmetic color selected from the group. According to the inkjet ink composition according to the present embodiment, in the inkjet recording method (inkjet printing method), high-definition decoration can be applied to a living body while suppressing adverse effects on the living body.

According to the inkjet ink composition according to the present embodiment, it is possible to suppress the occurrence of streaky printing defects. The ink-jet ink composition according to the present embodiment is also excellent in performance (setability) of suppressing peeling of printed matter on the surface of a printed matter.

The method for producing a printed matter according to the present embodiment includes a step of obtaining a printed matter by printing the ink composition for inkjet according to the present embodiment by an inkjet recording method.

The inkjet ink composition according to the present embodiment may be printed on a part of a living body (for example, a human body) such as a face, limbs, and body. The method for producing a printed matter according to the present embodiment may be an embodiment in which the inkjet ink composition according to the present embodiment is printed on a living body to obtain a printed matter.

The inkjet ink composition according to this embodiment may be printed on an object to be printed other than a living body. The method for producing a printed matter according to the present embodiment may be an embodiment in which the inkjet ink composition according to the present embodiment is printed on a printed matter other than a living body to obtain a printed matter.

The ink composition for inkjet includes a recording medium having excellent ink absorbency such as copy paper (PPC paper) generally used in a copying machine, a recording medium having an ink absorption layer, and ink absorbency. It is also possible to print on a non-absorbent recording medium having no ink, or a non-absorbable recording medium having low ink absorption. Examples of the recording medium include plain paper, cloth, cardboard, wood, inkjet paper, art paper, coated paper, finely coated paper, plastic film (resin film, polymer film) and the like.

The ink composition for inkjet can be printed on a base material such as a plastic film. Examples of the plastic film include polyester films such as polyethylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polyethylene film and polypropylene film; polyamide films such as nylon film; polystyrene film; polyvinyl alcohol film; polyvinyl chloride film; polycarbonate film. Polyacrylonitrile film; polylactic acid film and the like.

The ink jet composition may be used to obtain a transfer sheet capable of transferring a printed matter on a substrate to an adherend. The transfer sheet according to the present embodiment is a transfer sheet capable of transferring the printed matter on the substrate to the adherend, and the substrate, the printed matter obtained by the ink composition for inkjet according to the present embodiment, and the printed matter. The printed matter is arranged (printed) on the base material. The method for producing a transfer sheet according to the present embodiment is a method for producing a transfer sheet capable of transferring a printed matter on a substrate to an adherend, and the method for producing a printed matter according to the present embodiment allows the printed matter to be transferred onto the substrate. A step of obtaining a printed matter is provided. When the printed matter of the transfer sheet is transferred to the living body, high-definition decoration can be applied to the living body.

The ink composition according to the present embodiment includes a pigment dispersant (C), a binder resin (D), a compound (E) having a urea bond (hereinafter, sometimes referred to as “compound (E)”), and an organic solvent (F). , Surfactant (G), other additives and the like may be contained. Hereinafter, the constituent components of the ink composition including the aqueous medium (A) and the coloring material (B) will be described.

(Aqueous medium (A))
The ink composition according to this embodiment contains an aqueous medium (A) as a solvent. By using the water-based medium (A), the ink composition for inkjet can be used as the water-based ink. Water may be used alone as the aqueous medium (A), or a mixed solvent of water and the organic solvent (F) may be used. Specifically, as the water, pure water or ultrapure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water can be used. The content of the aqueous medium (A) may be 1 to 98% by mass or 5 to 95% by mass with respect to the total amount of the ink composition.

(Color material (B))
The coloring material (B) includes at least one cosmetic coloring material selected from the group consisting of cosmetic pigments (for example, cosmetic pigments) and cosmetic dyes (for example, cosmetic dyes). As the cosmetic coloring material, known and commonly used pigments, dyes and the like can be used. As the coloring material (B), a coloring agent in which the pigment is coated with a resin can also be used.

As the cosmetic coloring material, those used in ordinary cosmetics can be used. Cosmetic coloring materials include red 104 (1), red 201, red 202, red 220, red 223, red 226, red 227, red 228, red 230 (1), and blue. No. 1, Yellow No. 4, Yellow No. 5, Yellow No. 203, Iron Oxide, Navy Blue, Manganese Violet, Ultramarine Blue, Ultramarine Pink, Titanium Oxide, Carbon Black, Chromium Oxide, Chromium Hydroxide, Aluminum Hydroxide, Alumina, Glass Flake, Examples include mica-based pearl pigments, mica titanium, titanium oxide-coated mica, iron oxide-coated mica, talc, aluminum benzoate, aluminum, barium sulfate, synthetic gold mica, and composite oxides. C. I. Pigment No. These include CIAcid Red 92, CIPigment Red 57, CIPigment Red 57: 1, CIPigment Red 63: 1, CISolvent Red 43, CI Vat Red 1, CIAcid Red 33, CIPigment Red 4, CIAcid Red. 87, CIPigment Blue 78, CIPigment Yellow 100, CIPigment Yellow 104, CIPigment Yellow 115, CIPigmentYellow 42, CIPigment Black 11, CIPigmentRed 101, CIPigment Blue 29, CIPigmentViolet 15, CIPigment Green 18, etc. Be done.

The trade names of cosmetic coloring materials DIC Co., Ltd. or Sun Chemical Co., Ltd. include SunCROMA D & C Red 28 Al Lake, Soft-Tex D & C Red 28 Al Lake, SunCROMA D & C Red 6, SunCROMA D & C Red 7, SunCROMA D & C Red7 Ca Lake, SunCROMA D & C Red 34 Ca Lake, SunCROMA D & C Red 21, SunCROMA D & C Red30 Al Lake, SunCROMA D & C Red 30 Talc Lake, Soft-Tex D & C Red 30 Al Lake, SunCROMAD & C Red 33 Al Lake, SunCROMA D & C Red 36, SunCROMA D & C Red 22 Al Lake, SunCROMA FD & C Blue 1 Al Lake, Soft-Tex FD & C Blue 1 AlLake, SunCROMA FD & C Yellow 5 Al Lake, Soft-Tex FD & C Yellow 5 Al Lake, SunCROMA FD & C Yellow 6 Al Lake, SunCROMA D & C Yellow 10 AlLake, SunPURO Yellow Iron Oxide, SunCROMA Brown Iron Oxide, Soft-Tex Brown Iron Oxide, Soft-Tex Yellow Iron Oxide, SunCROMA BlackIron Oxide, Soft-Tex Black Iron Oxide, SunCROMA Red Iron Oxide, SunCROMA Russet Iron Oxide, Soft-Tex Red Iron Oxide, SunPURO Red Iron Oxide, SunPURO Maroon , SunPUROBronze, SunPURO Copper, Soft-TexIron Blue, SunCROMA Iron Blue, SunPURODeep Blue, SunCROMA Manganese Violet, SunCROMA Ultramarine Blue, SunCROMAUltramarine Pink, SunCROMA Ultramarine Blue AR, SunCRO MA Titanium Dioxide, SunPURO Titanium Dioxide, Soft-Tex Titanium Dioxide, SunPURO Ultra Fine White, SunPURO Fine White, SunPURO Silver White, SunPURO Sparkle White, SunPURO Pearl Silver, SunPURO Iridescent Gold, SunPURO Iridescent Red, SunPURO IridescentViolet, SunPURO Iridescent Blue, SunPURO Iridescent Green, SunPURO Blue, SunPUROBlue Green, SunPURO Green, SunPUROGold, SpectraFLEX Illusion, SunCROMAD & C Black 2, SunCROMA Chromium Oxide Green, SunCROMA Hydrated Chromium Oxide Green, MetalRayPolished Silver, MetalRay Liquid Metal, MetalRay Sterling Silver, MetalRay AntiqueMirror, INTENZA Electric Zest, INTENZA Passionate Kiss, INTENZA Radiant Rose, INTENZA Cerise, INTENZA Tourmaline, INTENZA Passion, INTENZA Creativity, INTENZA Rubis Velvet, INTENZA Flamingo, INTENZA Blue Lagoon, INTENZA Aqua Splash, INTENZA Envy, INTENZA Trust, INTENZA Blue Chambray, INTENZA , INTENZA Optimism, INTENZA Yellow Taffeta, etc.

The coloring material (B) may include a coloring material other than the cosmetic coloring material. The color material other than the cosmetic color material is not particularly limited, and inorganic pigments or organic pigments usually used in water-based gravure inks and water-based inkjet recording inks can be used. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), polycyclic pigments (phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments. , Isoindolinone pigments, quinophthalone pigments, etc.), lake pigments (basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like.

The content of the cosmetic coloring material is preferably 0.5 to 20% by mass with respect to the total amount of the ink composition from the viewpoint that it is easy to apply high-definition decoration to the living body while suppressing adverse effects on the living body. It is more preferably more than 0.5% by mass and 20% by mass or less, further preferably 1 to 20% by mass, particularly preferably 1.5 to 15% by mass, extremely preferably 2 to 10% by mass, and 3 to 8% by mass. It is very preferable, and 4 to 6% by mass is even more preferable.

The content of the cosmetic coloring material in the coloring material (B) is 80 mass with respect to the total amount of the coloring material (B) from the viewpoint that it is easy to apply high-definition decoration to the living body while suppressing adverse effects on the living body. % Or more is preferable, 90% by mass or more is more preferable, 95% by mass or more is further preferable, 98% by mass or more is particularly preferable, and 99% by mass or more is extremely preferable. The color material (B) may be substantially composed of a cosmetic color material (substantially 100% by mass of the color material (B) is a cosmetic color material).

The content of the coloring material (B) (the total amount of the coloring material including the cosmetic coloring material) is the total amount of the ink composition from the viewpoint of easily applying high-definition decoration to the living body while suppressing adverse effects on the living body. On the other hand, 0.5 to 20% by mass is preferable, more than 0.5% by mass and 20% by mass or less is more preferable, 1 to 20% by mass is further preferable, 1.5 to 15% by mass is particularly preferable, and 2 to 2% by mass. 10% by mass is extremely preferable, 3 to 8% by mass is very preferable, and 4 to 6% by mass is even more preferable.

(Pigment Dispersant (C))
Examples of the pigment dispersant (C) include polyvinyl alcohols; polyvinylpyrrolidones; acrylic resins such as acrylic acid-acrylic acid ester copolymers; styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene. Styrene-acrylic resins such as-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer; styrene-malein Aqueous resins such as acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers; salts of the aqueous resins and the like can be used. Pigment dispersants (C) include Ajinomoto Fine-Techno Co., Ltd.'s Ajispar PB series, Big Chemie Japan Co., Ltd.'s Disperbyk series, BASF's EFKA series, Japan Lubrizol Co., Ltd.'s SOLPERSE series, and Evonik's. TEGO series and the like can be used.

As the pigment dispersant (C), the following polymer (C1) can be used from the viewpoint that coarse particles can be remarkably reduced, and as a result, good ejection stability required when the ink composition is ejected by an inkjet recording method can be easily imparted. Is preferable.

As the polymer (C1), a polymer having an anionic group can be used. Above all, the number average molecular weight of 1000 to 6000 capable of forming fine particles in water when the solubility in water is 0.1 g / 100 mL or less and the neutralization rate of the anionic group by a basic compound is 100%. It is preferable to use the polymer of.

The solubility of the polymer (C1) in water can be defined as follows. That is, first, 0.5 g of the polymer (C1) having a particle size adjusted in the range of 250 μm to 90 μm using a sieve having a mesh size of 250 μm and 90 μm is sealed in a bag processed with a 400 mesh wire mesh and immersed in 50 mL of water. The mixture is gently stirred for 24 hours at a temperature of 25 ° C. After soaking for 24 hours, the 400 mesh wire mesh containing the polymer (C1) is dried in a dryer set at 110 ° C. for 2 hours. The change in mass of the 400 mesh wire mesh containing the polymer (C1) before and after immersion in water is measured, and the solubility is calculated by the following formula.
Solubility [g / 100 mL] = (Polymer-encapsulated 400-mesh wire mesh [g] before immersion-Polymer-encapsulated 400-mesh wire mesh [g] after immersion) x 2

Further, it can be determined as follows whether or not fine particles are formed in water when the neutralization rate of the anionic group by the basic compound is 100%.
(1) The acid value of the polymer (C1) is measured in advance by an acid value measuring method based on the JIS test method K0070-1992. Specifically, 0.5 g of the polymer (C1) is dissolved in tetrahydrofuran, and the acid value is determined by titrating with a 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.
(2) After adding 1 g of the polymer (C1) to 50 mL of water, a 0.1 mol / L potassium hydroxide aqueous solution that only neutralizes the obtained acid value by 100% is added to neutralize the obtained 100%.
(3) The 100% neutralized liquid is irradiated with ultrasonic waves in an ultrasonic cleaner (manufactured by SND Co., Ltd., ultrasonic cleaner US-102, 38 kHz self-excited oscillation) for 2 hours at a temperature of 25 ° C. After allowing it to stand, it is left at room temperature for 24 hours.

After leaving for 24 hours, using a liquid at a depth of 2 cm from the liquid surface as a sample liquid, a dynamic light scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., dynamic light scattering type particle size distribution measuring device "Microtrack particle size distribution" It is confirmed whether or not the fine particles are present by determining whether or not the light scattering information due to the formation of the fine particles can be obtained by using the meter UPA-ST150 ").

The particle size of the fine particles is preferably 5 to 1000 nm, more preferably 7 to 700 nm, still more preferably 10 to 500 nm, from the viewpoint of further improving the stability of the fine particles formed by the polymer (C1) in water. Further, the narrower the particle size distribution of the fine particles, the better the dispersion stability tends to be. However, even when the particle size distribution is wide, it is possible to obtain an ink composition having better dispersion stability than before. it can. The particle size and particle size distribution are the same as the method for measuring the fine particles. Dynamic light scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., dynamic light scattering type particle size measuring device "Microtrack particle size distribution meter" It can be measured using UPA-ST150 ").

The neutralization rate of the polymer (C1) can be determined by the following formula.
Neutralization rate (%) = {(mass of basic compound [g] × 56 × 1000) / (acid value of polymer (C1) [mgKOH / g] × equivalent of basic compound × mass of polymer (C1) [ g])} × 100

The acid value of the polymer (C1) can be measured based on the JIS test method K0070-1992. Specifically, it can be obtained by dissolving 0.5 g of a sample in tetrahydrofuran and titrating with a 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.

The number average molecular weight of the polymer (C1) can effectively suppress the aggregation of the coloring material (B) such as pigments in the aqueous medium (A), and the ink has good dispersion stability of the coloring material (B). From the viewpoint of easily obtaining the composition, 1000 to 6000 is preferable, 1300 to 5000 is more preferable, and 1500 to 4500 is further preferable. The number average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography), and specifically, a value measured under the following conditions.

[Measurement method of number average molecular weight (Mn)]
It was measured by the gel permeation chromatography (GPC) method under the following conditions.
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation are connected in series for use.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: Prepare a calibration curve using the following standard polystyrene.
{Standard polystyrene}
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

As the polymer (C1), a polymer that is insoluble or sparingly soluble in water in an unneutral state and forms fine particles in a 100% neutralized state can be used, and is a hydrophilic group. A polymer having a hydrophobic group in one molecule in addition to a certain anionic group can be used.

Examples of such a polymer include a block polymer having a polymer block having a hydrophobic group and a polymer block having an anionic group. In the polymer (C1), the number of the anionic groups and the solubility in water are not necessarily specified by the acid value or the number of anionic groups at the time of designing the polymer, and have, for example, the same acid value. Even polymers with a low molecular weight tend to have a high solubility in water, and those with a high molecular weight tend to have a low solubility in water. From this, the polymer (C1) is specified by its solubility in water.

The polymer (C1) may be a homopolymer, but is preferably a copolymer, and may be a random polymer, a block polymer, or an alternating polymer, and among them, a block polymer. Is preferable. The polymer (C1) may be a branched polymer, but is preferably a linear polymer.

The polymer (C1) is preferably a vinyl polymer from the viewpoint of design freedom, and methods for producing a vinyl polymer having a desired molecular weight and solubility characteristics include living radical polymerization, living cationic polymerization, and living anionic polymerization. It is preferably produced by using "living polymerization".

Among them, the polymer (C1) is preferably a vinyl polymer produced by using a (meth) acrylate monomer as one of the raw materials, and as a method for producing such a vinyl polymer, living radical polymerization or living anionic polymerization is used. In addition, living anionic polymerization is preferable from the viewpoint of the molecular weight of the block polymer and the more precise design of each segment.

As the polymer (C1) produced by living anionic polymerization, specifically, a polymer represented by the following general formula (c1) can be used.

In the general formula (c1), A ¹ represents an organic lithium initiator residue, A ² represents a polymer block having a hydrophobic group, A ³ represents a polymer block having an anionic group, and n represents a polymer block having an anionic group. , 1-5, where B represents an aromatic group or an alkyl group.

In the general formula (c1), A ¹ represents an organolithium initiator residue. Specific examples of the organolithium initiator (polymerization initiator) include methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.), and pentyl. Alkyllithium such as lithium, hexyllithium, methoxymethyllithium, etoshikimethyllithium; benzyllithium, α-methylstyryllithium, 1,1-diphenyl-3-methylpentyllithium, 1,1-diphenylhexyllithium, phenylethyl Phenylalkylene lithium such as lithium; alkenyllithium such as vinyllithium, allyllithium, propenyllithium, butenyllithium; alkynyllithium such as ethynyllithium, butynyllithium, pentynyllithium, hexynyllithium; Aryllithium; heterocyclic lithium such as 2-thienyllithium, 4-pyridyllithium, 2-quinolyllithium; alkyllithium-magnesium complex such as tri (n-butyl) magnesium lithium, trimethylmagnesium lithium and the like can be mentioned.

In the organolithium initiator, the bond between the organic group and lithium is cleaved to generate an active terminal on the organic group side, and polymerization is started from there. Therefore, an organic group derived from organolithium is bonded to the terminal of the obtained polymer. In the present specification, the organic group derived from organolithium bonded to the polymer terminal is referred to as "organolithium initiator residue". For example, in the case of a polymer using methyllithium as an initiator, the organolithium initiator residue is a methyl group, and in the case of a polymer using butyllithium as an initiator, the organolithium initiator residue is a butyl group. ..

In the general formula (c1), A ² represents a polymer block having a hydrophobic group. As described above, A ² is preferably a group having a high adsorption to the pigment when in contact with the pigment, in addition to the purpose of balancing an appropriate solubility. From the same viewpoint, A ² is an aromatic ring or an aromatic ring. It is preferably a polymer block having a structural unit derived from a monomer having a heterocycle. The polymer block having a structural unit derived from a monomer having an aromatic ring or a heterocycle is specifically a monomer having an aromatic ring such as a styrene monomer or a monomer having a heterocycle such as a vinylpyridine monomer. It is a polymer block of a homopolymer or a copolymer obtained by homopolymerizing or copolymerizing.

Examples of the monomer having an aromatic ring include styrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, p-tert-butoxystyrene, m-tert-butoxystyrene, and the like. Styrene-based monomers such as p-tert- (1-ethoxymethyl) styrene, m-chlorostyrene, p-chlorostyrene, p-fluorostyrene, α-methylstyrene, p-methyl-α-methylstyrene, vinylnaphthalene, Vinyl anthracene and the like can be mentioned. Examples of the monomer having a heterocycle include vinylpyridine-based monomers such as 2-vinylpyridine and 4-vinylpyridine. Each of the monomers having an aromatic ring or a heterocycle can be used alone or in combination of two or more.

In the general formula (c1), ^{A 3} represents a polymer block having an anionic group. A ³ is another object to provide a moderate solubility as described above, there is a purpose of imparting dispersion stability in water when a pigment dispersion.

The anionic groups in the polymer block A ^3, carboxyl group, sulfonic acid group and a phosphoric acid group. Of these, a carboxyl group is preferable from the viewpoints of ease of preparation, abundance of monomer varieties, availability, and the like. Further, the two carboxyl groups may be an acid anhydride group obtained by intramolecular or intermolecular dehydration condensation.

Introduction of the anionic group A ³ is not particularly limited, for example, when the anionic group is a carboxyl group, (meth) homopolymer or copolymer obtained by copolymerizing a homopolymer or other monomers acrylic acid Polymer block (PB1) of the above, which is a homopolymer obtained by deprotecting a (meth) acrylate having a reproducible protective group as an anionic group by homopolymerization or copolymerization with another monomer. Alternatively, the copolymer may be a polymer block (PB2) in which some or all of the protective groups reproducible to the anionic group are regenerated into an anionic group.

The use of a polymer block A ³ (meth) acrylic acid or (meth) acrylate, specifically, (meth) acrylic acid, (meth) acrylate, (meth) acrylate, (meth) acrylic acid iso-propyl, allyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) N-amyl acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-lauryl (meth) acrylate , (Meta) n-tridecyl acrylate, (meth) n-stearyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-tert-butyl (meth) acrylate Cyclohexyl, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydro (meth) acrylate Flufuryl, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, ( Tetrafluoropropyl acrylate, pentafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, pentadecafluorooctyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, N, N- Dimethyl (meth) acrylamide, (meth) acryloylmorpholine, (meth) acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) Acrylate, Polypropylene glycol-Polybutylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, Octoxypolyethylene glycol (meth) acrylic Poly, such as lauroxy polyethylene glycol (meth) acrylate, stearoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol-polypropylene glycol (meth) acrylate. Examples thereof include alkylene oxide group-containing (meth) acrylate. These monomers may be used alone or in admixture of two or more.

In the living anionic polymerization method, when the monomer used is a monomer having a group having an active proton such as an anionic group, the active end of the living anionic polymer polymer immediately reacts with the group having these active protons and is deactivated. , Polymer is difficult to obtain. In living anionic polymerization, it is difficult to polymerize a monomer having a group having an active proton as it is. Therefore, the active proton is polymerized by polymerizing the group having an active proton in a protected state and then deprotecting the protecting group. It is preferable to regenerate the group having.

For this reason, in the polymer block A ^3, it is preferable to use a monomer containing a (meth) acrylate having an anionic renewable protecting group group by deprotection. By using the monomer, it is possible to prevent the above-mentioned inhibition of polymerization at the time of polymerization. Further, the anionic group protected by the protecting group can be regenerated into the anionic group by deprotecting after obtaining the block polymer.

For example, when the anionic group is a carboxyl group, the carboxyl group can be regenerated by esterifying the carboxyl group and deprotecting it by hydrolysis or the like as a subsequent step. In this case, the protective group that can be converted into a carboxyl group is preferably a group having an ester bond, and is, for example, a primary alkoxycarbonyl such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an n-butoxycarbonyl group. Group; Secondary alkoxycarbonyl group such as isopropoxycarbonyl group, sec-butoxycarbonyl group; Tertiary alkoxycarbonyl group such as t-butoxycarbonyl group; Phenylalkoxycarbonyl group such as benzyloxycarbonyl group; ethoxyethylcarbonyl group Such as an alkoxyalkylcarbonyl group and the like.

When the anionic group is a carboxyl group, the monomers that can be used include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and sec. -Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate ) Acrylate), tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecil (meth) acrylate, icosanyl (meth) ) Alkyl (meth) acrylates such as acrylates; phenylalkylene (meth) acrylates such as benzyl (meth) acrylates; alkoxyalkyl (meth) acrylates such as ethoxyethyl (meth) acrylates and the like. These (meth) acrylates can be used alone or in combination of two or more. Further, among these (meth) acrylates, one or more selected from the group consisting of t-butyl (meth) acrylate and benzyl (meth) acrylate is preferable from the viewpoint of easy conversion reaction to a carboxyl group, and it is industrialized. From the viewpoint of easy availability, t-butyl (meth) acrylate is more preferable.

In the general formula (c1), B represents an aromatic group or an alkyl group. As the alkyl group, an alkyl group having 1 to 10 carbon atoms can be used. Further, n represents an integer of 1 to 5.

In the living anion polymerization method, when an attempt is made to directly polymerize a (meth) acrylate monomer at the active terminal of a styrene-based polymer having strong nucleophilicity, it may not be possible to polymerize due to a nucleophilic attack on the carbonyl carbon. Therefore, ^{when the (meth) acrylate monomer is polymerized on A 1 to} A ² , a reaction modifier can be used to adjust the nucleophilicity, and then the (meth) acrylate monomer can be polymerized. B in the general formula (c1) is a group derived from the reaction modifier. Specific examples of the reaction modifier include diphenylethylene, α-methylstyrene, p-methyl-α-methylstyrene and the like.

The living anion polymerization method can be carried out by a batch method as used in the conventional free radical polymerization by adjusting the reaction conditions, or may be a method of continuous polymerization by a microreactor. In the microreactor, since the mixture of the polymerization initiator and the monomer is good, the reaction starts at the same time, the temperature is uniform, and the polymerization rate can be made uniform, so that the molecular weight distribution of the produced polymer can be narrowed. At the same time, since the growth end is stable, it becomes easy to produce a block copolymer in which both components of the block are not mixed. Moreover, since the controllability of the reaction temperature is good, it is easy to suppress side reactions.

A general method of living anionic polymerization using a microreactor will be described with reference to FIG. 1, which is a schematic diagram of the microreactor.

First, the first monomer and the polymerization initiator that initiates the polymerization are introduced from the tube reactors P1 and P2 into a T-shaped micromixer M1 provided with a flow path capable of mixing a plurality of liquids, respectively, and the T-shaped micro is introduced. In the mixer M1, the first monomer is subjected to living anionic polymerization to form the first polymer (step 1).

Next, the obtained first polymer is moved to a T-shaped micromixer M2, and the growth end of the obtained polymer is trapped in the mixer M2 by a reaction modifier introduced from the tube reactor P3. Then, the reaction is adjusted (step 2). At this time, the number of n in the general formula (c1) can be controlled by the type and amount of the reaction modifier.

Next, the first polymer whose reaction was adjusted in the T-shaped micromixer M2 was moved to the T-shaped micromixer M3, and the second monomer introduced from the tube reactor P4 in the mixer M3. And the first polymer whose reaction has been adjusted are continuously subjected to living anionic polymerization (step 3).

Then, the reaction is quenched with a compound having an active proton (methanol, etc.) to produce a block copolymer.

When the polymer (C1) represented by the general formula (c1) is produced in the microreactor, a monomer having a hydrophobic group (for example, a monomer having an aromatic ring or a heterocycle) is used as the first monomer. Then, by reacting with an organic lithium initiator as a polymerization initiator ^{, a polymer block having a hydrophobic group of A 2} (for example, a polymer block having a structural unit derived from a monomer having an aromatic ring or a heterocycle). (An organic group, which is an organic lithium initiator residue of ^{A 1} , is bonded to one end of the polymer block A ^2).

Next, after adjusting the reactivity of the growth terminal using a reaction modifier, a monomer containing a (meth) acrylate having a renewable protecting group in the anionic group is reacted as the second monomer to react with the polymer. Get a block.

Thereafter, by reproducing the anionic group by deprotection reaction such as hydrolysis, the A ^{3 (i.e.,} a polymer block containing an anionic group) is obtained.

A method for regenerating an ester bond of a regenerative protecting group into an anionic group by a deprotection reaction such as hydrolysis will be described in detail as follows.

The hydrolysis reaction of an ester bond proceeds under both acidic and basic conditions, but the conditions are slightly different depending on the group having the ester bond. For example, when the group having an ester bond is a primary alkoxycarbonyl group such as a methoxycarbonyl group or a secondary alkoxycarbonyl group such as an isopropoxycarbonyl group, it can be hydrolyzed under basic conditions. A carboxyl group can be obtained. At this time, examples of the basic compound under basic conditions include metal hydroxides such as sodium hydroxide and potassium hydroxide.

When the group having an ester bond is a tertiary alkoxycarbonyl group such as a t-butoxycarbonyl group, a carboxyl group can be obtained by hydrolysis under acidic conditions. At this time, examples of the acidic compound under acidic conditions include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; breathed acids such as trifluoroacetic acid; and Lewis acids such as trimethylsilyl trifurate. The reaction conditions for hydrolysis of the t-butoxycarbonyl group under acidic conditions are disclosed, for example, in "The Chemical Society of Japan, 5th Edition, Experimental Chemistry Course 16 Synthesis of Organic Compounds IV".

Examples of the method for converting the t-butoxycarbonyl group into a carboxyl group include a method using a cation exchange resin instead of the above acid. The cation exchange resin, for example, carboxyl group in the side chain of the polymer chain (-COOH), resins having a sulfo group _(-SO 3 H) acid groups and the like. Among these, a strongly acidic cation exchange resin having a sulfo group in the side chain of the resin is preferable because the reaction can proceed quickly. Examples of commercially available cation exchange resins include the strongly acidic cation exchange resin "Amberlite" manufactured by Organo Corporation. From the viewpoint of effective hydrolysis, the amount of the cation exchange resin used is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the polymer represented by the general formula (c1). preferable.

When the group having an ester bond is a phenylalkoxycarbonyl group such as a benzyloxycarbonyl group, it can be converted to a carboxyl group by performing a hydrogenation reduction reaction. At this time, as a reaction condition, the phenylalkoxycarbonyl group can be quantitatively regenerated into a carboxyl group by reacting with hydrogen gas as a reducing agent in the presence of a palladium catalyst such as palladium acetate at room temperature.

As described above, since the reaction conditions during the conversion to a carboxyl group depending on the kind of group having an ester bond are different, for example, t- butyl (meth) as a raw material of A ³ and acrylate and n- butyl (meth) acrylate The polymer obtained by copolymerization using the above will have a t-butoxycarbonyl group and an n-butoxycarbonyl group. Here, under acidic conditions in which the t-butoxycarbonyl group is hydrolyzed, the n-butoxycarbonyl group is not hydrolyzed, so that only the t-butoxycarbonyl group can be selectively hydrolyzed to be deprotected to the carboxyl group. It becomes. Thus, a raw material monomer of A ^3, it is possible to the acid value of the adjustment of the hydrophilic block (A ³⁾ by appropriately selecting a monomer containing a (meth) acrylate having a renewable protecting group an anionic group.

From the viewpoint of improving the stability of the aqueous pigment dispersion in which the pigment is dispersed in water by the polymer (C1), the polymer block (A ² ) and the polymer block (A 2) are used in the polymer (C1) represented by the general formula (c1). a ³⁾ and is not a random copolymer bound arranged at random, it is advantageous more the polymer block is a block copolymer linked regularly become certain length chunks. The aqueous pigment dispersion is a raw material that can be used in the production of an ink composition, and is a liquid in which a pigment is dispersed in water at a high concentration using a polymer (C1). The molar ratio A ² : A ³ of the polymer block (A ² ) and the polymer block (A ³ ) is a viewpoint that it is easy to maintain good ejection stability required when ejecting an ink composition by, for example, an inkjet recording method, and From the viewpoint of easily obtaining an ink composition capable of producing a printed matter having further excellent color development properties, 100: 10 to 100: 500 is preferable, and 100: 10 to 100: 450 is more preferable.

In the polymer (C1) represented by the general formula (c1), the ^{number of monomers having an aromatic ring or a heterocycle giving the polymer block (A 2} ) is preferably 5 to 40, more preferably 6 to 30, and 7 to 7. 25 is more preferred. The number of anionic groups constituting the polymer block ^{(A 3)} is preferably from 3 to 20, more preferably from 4 to 17, more preferably 5 to 15.

The molar ratio of the polymer block (A ² ) and the polymer block (A ^{3 ) A 2} : A ³ constitutes the number of moles of the aromatic ring or the heterocycle constituting the polymer block (A ^{2 ) and the polymer block (A 3} ). When expressed in terms of the molar ratio with the number of moles of the anionic group to be used, 100: 7.5 to 100: 400 is preferable.

The acid value of the polymer (C1) represented by the general formula (c1) has a viewpoint that it is easy to maintain good ejection stability required when ejecting an ink composition by an inkjet recording method, and scratch resistance and the like. From the viewpoint that an ink composition capable of producing an even more excellent printed matter can be easily obtained, 40 to 400 mgKOH / g is preferable, 40 to 300 mgKOH / g is more preferable, and 40 to 190 mgKOH / g is further preferable. The acid value of the polymer (C1) was determined by the same acid value measuring method as the method for measuring the fine particles of the polymer (C1).

In the ink composition according to the present embodiment, the anionic group of the polymer (C1) is preferably neutralized.

As the basic compound that neutralizes the anionic group of the polymer (C1), any known and commonly used compound can be used. For example, an inorganic basic substance such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Alternatively, organic basic compounds such as ammonia, triethylamine and alkanolamine can be used.

The amount of neutralization of the polymer (C1) present in the aqueous pigment dispersion need not be 100% neutralized with respect to the acid value of the polymer. Specifically, the polymer (C1) is preferably neutralized so that the neutralization rate is 20 to 200%, and more preferably 80 to 150%.

(Binder resin (D))
Examples of the binder resin (D) include polyvinyl alcohol, gelatin, polyethylene oxide, polyvinyl pyrrolidone, acrylic resin, urethane resin, dextran, dextrin, color ginan (κ, ι, λ, etc.), agar, purulan, and water-soluble polyvinyl. Butyral, hydroxyethyl cellulose, carboxymethyl cellulose and the like can be used alone or in combination of several. Among them, as the binder resin (D), it is preferable to use an acrylic resin, and it is more preferable to use an acrylic resin having an amide group.

The ink composition containing the binder resin (D) is a coagulated product because the ink composition is recirculated to the ejection port even when the ink composition at the ink ejection port is solidified due to solvent evaporation due to drying. Is excellent in the property (redispersibility) that can be easily dispersed in the ink composition. As a result, when ejecting from the inkjet head, even if the ejection is interrupted for a certain period of time and then restarted, it is unlikely that the ejected droplets are bent or the ejection port is clogged, resulting in streaky printing defects. It is easy to prevent the occurrence effectively.

As the acrylic resin having an amide group, a polymer of an acrylic monomer having an amide group and other monomers used as needed can be used.

Examples of acrylic monomers having an amide group include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-methylol (meth) acrylamide. , N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N, N -Dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, hydroxyethyl (meth) acrylamide, acrylic amide, N, N-dimethyl (meth) acrylic amide and the like can be used.

Examples of other monomers that can be used in the production of the acrylic resin include (meth) acrylic acid and alkali metal salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2 -(Meta) acrylic acid ester compounds such as ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate; (meth) acrylonitrile, 2-dimethylaminoethyl (meth) acrylate, glycidyl ( Acrylic monomers such as meta) acrylate; aromatic vinyl compounds (styrene, α-methylstyrene, p-tert-butylstyrene, vinylnaphthalene, vinylanthracene, etc.), vinyl sulfonic acid compounds (vinyl sulfonic acid, styrene sulfonic acid) Etc.), vinyl pyridine compounds (2-vinylpyridine, 4-vinylpyridine, naphthylvinylpyridine, etc.), vinyltriethoxysilane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 − Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be used.

As the other monomer, a monomer having an aromatic group such as styrene or benzyl (meth) acrylate is preferable from the viewpoint of further improving the affinity with the pigment.

The acrylic resin having an amide group imparts the effect of improving redispersibility to the ink composition and is excellent in dispersion stability in the aqueous medium (A). In the acrylic resin having an amide group, the amount of the acrylic monomer having an amide group used determines the redispersibility of the ink composition and the dispersion stability of the constituent components of the ink composition in the aqueous medium (A). From the viewpoint of further improving the above, 0.5 to 5% by mass is preferable, 0.5 to 4% by mass is more preferable, and 1.5 to 1% to the total amount of the monomers used in the production of the acrylic resin. 3% by mass is more preferable.

The acrylic resin may contain a component that is insoluble in tetrahydrofuran (THF), which is a developing solvent for measuring the molecular weight by gel permeation chromatography, and whose molecular weight is difficult to measure, but THF at 25 ° C. The content of the insoluble component is preferably less than 20% by mass, more preferably less than 5% by mass, and further preferably not containing the THF insoluble component.

The number average molecular weight of the acrylic resin (for example, the acrylic resin dissolved in THF) is preferably 1000 to 100,000, more preferably 2000 to 100,000. The weight average molecular weight of the acrylic resin is preferably 30,000 to 1,000,000, more preferably 50,000 to 1,000,000.

As the binder resin (D), for example, polyolefin can be used.

As the polyolefin, a homopolymer or a copolymer of a monomer containing an olefin-based monomer as a main component can be used. As the olefin-based monomer, for example, α-olefins such as ethylene, propylene, butene, hexene, methylbutene, methylpentene and methylhexene; and cyclic olefins such as norbornene can be used.

As the polyolefin, an oxidized polyolefin can also be used. As the oxidized polyolefin, for example, a polyolefin in which an oxygen atom is introduced into the molecule by thermal decomposition, chemical decomposition using an acid, an alkaline component, or the like can be used. The oxygen atom constitutes, for example, a polar carboxyl group or the like.

The melting point of the polyolefin is preferably 90 to 200 ° C, more preferably 120 ° C or higher and lower than 160 ° C. In these cases, even when the printed matter is superposed immediately after printing, it is possible to impart good settability in which the ink composition on the surface of the object to be printed does not peel off and excellent scratch resistance. The melting point of polyolefin refers to a value measured by a melting point measuring device conforming to JIS K 0064.

As described above, the polyolefin is preferably present in a state of being dissolved or dispersed in a solvent such as an aqueous medium (A), and more preferably in a state of an emulsion dispersed in a solvent such as an aqueous medium (A).

In that case, the average particle size of the polyolefin particles formed by the polyolefin is from the viewpoint that it is easy to achieve both good ejection stability of the ink composition and good settability after printing when printing by the inkjet recording method. It is preferably 10 to 200 nm, more preferably 30 to 150 nm. The average particle size of the polyolefin (A) is a value measured by a dynamic light scattering method using a Microtrack UPA particle size distribution meter manufactured by Nikkiso Co., Ltd.

The binder resin (D) is used with respect to the total amount of the ink composition from the viewpoint of easily preventing the occurrence of streaky printing defects, improving the print density and scratch resistance of the printed matter, and imparting good gloss. 2 to 7% by mass is preferable, and 2 to 6% by mass is more preferable. Further, in the ink composition containing the binder resin (D) in these ranges, the binder resin (D) is crosslinked to form a strong film through a heating step after printing, so that the scratch resistance of the printed matter is further improved. It can be further improved. Further, even when water is dropped on the printed matter or when it is rubbed with a cloth or the like containing water, the ink composition on the surface of the printed matter does not peel off, and good water resistance can be imparted.

In the ink composition according to the present embodiment, the binder resin (D) and the compound (E) can be used in combination. By using the binder resin (D) and the compound (E) in combination, it is easy to impart good settability of printed matter and excellent scratch resistance.

(Compound (E) having a urea bond)
As the compound (E) having a urea bond, one or more selected from the group consisting of urea and a urea derivative can be used. Urea and urea derivatives have a high moisturizing function and function as a moisturizer, so that they prevent the ink composition from drying and solidifying at the ink ejection port of the inkjet head, and it is easy to secure excellent ejection stability. It has the effect of easily reducing the occurrence of printing defects. Further, since water is easily released when the urea and the urea derivative are heated, when a urea or a urea derivative is used, the ink composition is heated and dried after printing from the viewpoint of easily obtaining a printed matter having even better settability. Is preferable.

Examples of the urea derivative include ethylene urea, propylene urea, diethyl urea, thiourea, N, N-dimethylurea, hydroxyethylurea, hydroxybutylurea, ethylenethiourea, diethylthiourea, etc., and these are one type alone or two types. The above combinations can be used. Among them, as the compound (E), one or more selected from the group consisting of urea, ethylene urea and 2-hydroxyethyl urea is preferable from the viewpoint of easily obtaining a printed matter having excellent settability.

The content of the compound (E) is 1 with respect to the total amount of the ink composition from the viewpoint of ejection stability required when the ink composition is ejected by the inkjet recording method and easy to obtain a printed matter having excellent settability. -20% by mass is preferable, 2 to 15% by mass is more preferable, and 3 to 10% by mass is further preferable.

When the ink composition contains the binder resin (D) and the compound (E), the mass ratio of the binder resin (D) to the compound (E) [binder resin (D) / compound (E)] is the settability of the printed matter. From the viewpoint of easily obtaining the improving effect, 1/6 to 6/1 is preferable, 1/6 to 3/1 is more preferable, and 1/5 to 1/1 is further preferable.

(Organic solvent (F))
Examples of the organic solvent (F) include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone; methanol, ethanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-methoxyethanol and the like. Alcohols; ethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane; dimethylformamide, N-methylpyrrolidone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene Glycos such as glycols; diols such as butanediol, pentanediol, hexanediol, and diols of the same family; glycol esters such as propylene glycol laurate; diethylene glycol monoethyl, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol ether. , Dipropylene glycol ethers, and glycol ethers such as cellosolve containing triethylene glycol ethers; methanol, ethanol, isopropyl alcohol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and other butyl alcohols, pentyl alcohols. , Alcohols such as alcohols of the same family; sulfolanes; lactones such as γ-butyrolactone; lactams such as N- (2-hydroxyethyl) pyrrolidone, etc., and these may be used alone or in combination of two or more. Can be used.

The organic solvent (F) has a boiling point of 100 to 200 in addition to the above-mentioned ones from the viewpoint of easily obtaining a quick-drying effect in which the discharged droplets land on the surface of the object to be printed and then quickly dry on the object to be printed. A water-soluble organic solvent (f1) having a vapor pressure of 0.5 hPa or more at 20 ° C. is preferable.

Examples of the water-soluble organic solvent (f1) include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butyl acetate, ethylene glycol monomethyl ether, and ethylene glycol. Monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate , Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, 4-methoxy-4-methyl-2-pentanone, ethyl lactate, etc., and these may be used alone or in combination of two or more. Can be done.

Among them, the water-soluble organic solvent (f1) has a viewpoint that it is easy to maintain good dispersion stability of the ink composition, and for example, deterioration of the ink ejection nozzle provided in the inkjet device due to the influence of the solvent contained in the ink composition. From the viewpoint of easily suppressing the above, it is preferable to use a water-soluble organic solvent having _{a hydrogen bond term δ H of} HSP (Hansen solubility parameter) in the range of 6 to 20.

Specific examples of the water-soluble organic solvent having the hydrogen bond term of HSP in the above range include 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. , Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monopropyl ether. More than one species is preferable, and one or more species selected from the group consisting of 3-methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol are more preferable.

As an organic solvent that can be used in combination with the aqueous medium (A), the effect of quick-drying the ink on the object to be printed and the effect of preventing the ink composition from drying and solidifying at the ink ejection port can be easily compatible with each other. One or more selected from the group consisting of propylene glycol (f2) and glycerin, glycerin derivative, diglycerin and diglycerin derivative in addition to the water-soluble organic solvent (f1) or together with the water-soluble organic solvent (f1). It is preferable to use it in combination with an organic solvent (f3).

Examples of the organic solvent (f3) include glycerin, diglycerin, polyglycerin, diglycerin fatty acid ester, polyoxypropylene (n) polyglyceryl ether represented by the following general formula (f1), and the following general formula (f2). The polyoxyethylene (n) polyglyceryl ether and the like to be used can be used alone or in combination of two or more. Among them, the organic solvent (f3) is excellent in settability of printed matter, and from the viewpoint of easily obtaining the effect of preventing the ink composition from drying and solidifying at the ink ejection port, glycerin and polyoxypropylene having n = 8 to 15 are obtained. (N) One or more selected from the group consisting of polyglyceryl ether is preferable.

In the general formula (f1) and the general formula (f2), m1, m2, n1, n2, p1, p2, q1 and q2 each independently represent an integer of 1 to 10.

The content of the organic solvent (F) is 1 to 30 with respect to the total amount of the ink composition from the viewpoint that the printed matter is excellent in settability and the effect of preventing the ink composition from drying or solidifying at the ink ejection port is easily obtained. It is preferably by mass, more preferably 5 to 25% by mass.

The mass ratio of the water-soluble organic solvent (f1) to propylene glycol (f2) [water-soluble organic solvent (f1) / propylene glycol (f2)] has excellent settability of printed matter, and can dry the ink composition at the ink ejection port. From the viewpoint of easily obtaining the effect of preventing solidification, 1/25 to 2/1 is preferable, 1/25 to 1/1 is more preferable, and 1/20 to 1/1 is further preferable.

The mass ratio of propylene glycol (f2) to the organic solvent (f3) [propylene glycol (f2) / organic solvent (f3)] has excellent settability of printed matter and prevents the ink composition from drying or solidifying at the ink ejection port. From the viewpoint of easily obtaining the effect, 1/4 to 8/1 is preferable, 1/3 to 6/1 is more preferable, and 1/2 to 5/1 is further preferable.

(Surfactant (G))
By using the surfactant (G), the ink composition ejected from the ejection port of the inkjet head tends to get wet and spread well on the surface after landing on the object to be printed, so that streaky printing defects occur. Easy to prevent. Further, by using the surfactant (G), the leveling property of the ink composition can be easily improved by lowering the surface tension of the ink composition.

As the surfactant (G), various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used, and streaky printing defects occur. From the viewpoint of easily suppressing the above, one or more selected from the group consisting of an anionic surfactant and a nonionic surfactant is preferable.

Anionic surfactants include alkylbenzene sulfonates, alkylphenyl sulfonates, alkylnaphthalene sulfonates, higher fatty acid salts, higher fatty acid ester sulfates, higher fatty acid ester sulfonates, and higher alcohol ether sulfates. Examples thereof include ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and the like. Specific examples include dodecylbenzene sulfonate, isopropylnaphthalene sulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol disulfonate and the like.

Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, and poly. Oxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, fatty acid alkylolamide, alkylalkanolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, polyethylene glycol Examples thereof include polypropylene glycol block copolymers, among which polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, and sorbitan fatty acid ester. , Polyoxyethylene sorbitan fatty acid ester, fatty acid alkylolamide, acetylene glycol, oxyethylene adduct of acetylene glycol, and one or more selected from the group consisting of polyethylene glycol polypropylene glycol block copolymer.

The ink composition according to the present embodiment preferably contains an acetylene-based surfactant from the viewpoint of easily suppressing the occurrence of streaky printing defects. The acetylene-based surfactant is a surfactant having an acetylene structure in the molecule. The acetylene-based surfactant is preferably contained at least one selected from the group consisting of acetylene glycol and an oxyethylene adduct of acetylene glycol from the viewpoint of easily suppressing the occurrence of streak-like printing defects.

Other surfactants include silicone-based surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylic acid salts, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers; Biosurfactants such as spicrysporic acid, ramnolipide, and lysolecithin can also be used.

The content of the acetylene-based surfactant is preferably 80 to 100% by mass, preferably 80 to 100% by mass, based on the total amount of the surfactant (G), from the viewpoint of easily suppressing the occurrence of streak-like printing defects. 9% by mass is more preferable, 90 to 99.5% by mass is further preferable, and 95 to 99.3% by mass is particularly preferable.

The carbon number of the main chain of the acetylene-based surfactant is preferably 20 or less, more preferably 18 or less, further preferably 15 or less, and particularly preferably 13 or less, from the viewpoint of easily suppressing the occurrence of streak-like printing defects. .. The carbon number of the main chain of the acetylene-based surfactant is preferably 5 or more, more preferably 8 or more, further preferably 10 or more, and particularly 11 or more, from the viewpoint of easily suppressing the occurrence of streak-like printing defects. Preferably, 12 or more is extremely preferable. The carbon number of the main chain is the carbon number of the longest molecular chain (for example, a carbon chain) containing an acetylene bond.

The HLB value of the surfactant (G) stabilizes the state in which the surfactant (G) is dissolved in the ink composition containing water as the main solvent, from the viewpoint that it is easy to suppress the occurrence of streak-like printing defects. From the viewpoint of easy maintenance, 1 to 12 is preferable, 1 to 10 is more preferable, 2 to 9 is further preferable, 3 to 8 is particularly preferable, and 4 to 8 is extremely preferable. The HLB value of the acetylene-based surfactant is stable from the viewpoint of easily suppressing the occurrence of streak-like printing defects and the state in which the surfactant (G) is dissolved in an ink composition containing water as a main solvent. From the viewpoint of easy maintenance, it is preferable to be in these ranges. The HLB value of the surfactant (G) can be determined by, for example, the Griffin method.

The content of the surfactant (G) is preferably 0.001 to 5% by mass, more preferably 0.001 to 3% by mass, and further preferably 0.001 to 2% by mass with respect to the total amount of the ink composition. Preferably, 0.01 to 2% by mass is particularly preferable, 0.1 to 2% by mass is extremely preferable, 0.5 to 2% by mass is very preferable, 0.8 to 2% by mass is even more preferable, and 1 to 1% by mass is preferable. 1.6% by mass is more preferable. The ink composition containing the surfactant (G) at these contents has good wettability on the surface of the printed matter of the ejected droplets, and tends to have a sufficient wettling spread on the printed matter. , It is easy to obtain the effect of preventing the occurrence of streaky printing defects. Further, the ink composition containing the surfactant (G) in each of the above ranges can easily obtain the effect of improving the leveling property of the coating film. From the same viewpoint, the content of the acetylene-based surfactant is preferably in each of the above ranges.

(Other additives)
The ink composition according to the present embodiment includes a wetting agent (drying inhibitor), a penetrant, a preservative (for example, ACTICIDE MV4 manufactured by So Japan Co., Ltd.), a viscosity regulator, and a pH regulator (for example, triethanolamine). , Chelating agents, plasticizers, antioxidants, UV absorbers and other additives can be included.

As the wetting agent, it can be used for the purpose of preventing the ink composition from drying in the ejection nozzle of the inkjet head. The content of the wetting agent is preferably 3 to 50% by mass with respect to the total amount of the ink composition.

The wetting agent is preferably one that is compatible with water and has an effect of preventing clogging of the ejection port of the inkjet head. For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 2000 or less, and dipropylene glycol are preferable. , Tripropylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, mesoerythritol, pentaerythritol and the like.

Examples of the penetrant include lower alcohols such as ethanol and isopropyl alcohol; ethylene oxide adducts of alkyl alcohols such as ethylene glycol hexyl ether and diethylene glycol butyl ether; and propylene oxide adducts of alkyl alcohols such as propylene glycol propyl ether. The content of the penetrant is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably substantially free of the penetrant, based on the total amount of the ink composition.

Hereinafter, the present invention will be described with reference to Experimental Examples, but the present invention is not limited to these Experimental Examples.

<Preparation of polymer (P-1)>
A hexane solution of normal butyllithium (BuLi) and a styrene solution in which styrene is previously dissolved in tetrahydrofuran are introduced into a T-shaped micromixer M1 from tube reactors P1 and P2 shown in FIG. Obtained coalescence.
Next, the polymer obtained in the above step was moved to the T-shaped micromixer M2 through the tube reactor R1 shown in FIG. 1, and the growth end of the polymer was introduced from the tube reactor P3 as a reaction modifier (α). -Methylstyrene (α-MeSt)) trapped.
Next, the tert-butyl methacrylate solution in which tert-butyl methacrylate was previously dissolved in tetrahydrofuran was introduced into the T-shaped micromixer M3 from the tube reactor P4 shown in FIG. 1 and moved through the tube reactor R2. Living anionic polymerization reaction was carried out continuously with the coalescence. Then, the block copolymer (PA-1) composition was produced by quenching the living anionic polymerization reaction by supplying methanol. The block copolymer (PA-1) composition was recovered from the tube reactor R3.

When producing the block copolymer (PA-1) composition, the reaction temperature was set to 24 ° C. by burying the entire microreactor shown in FIG. 1 in a constant temperature bath. The molar ratio of the monomers constituting the block copolymer (PA-1) composition obtained by the above method is (BuLi / styrene / α-methylstyrene / tert-butylmethacrylate) = 1.0 / 12.0 /. It was 2.0 / 8.1. The obtained block copolymer (PA-1) composition is hydrolyzed by treating it with a cation exchange resin, then distilled off under reduced pressure, and the obtained solid is pulverized to form a powdery polymer (). P-1) was obtained.

The physical characteristic values of the obtained polymer (P-1) were measured as follows.

(Measurement of number average molecular weight (Mn))
It was measured by the gel permeation chromatography (GPC) method under the following conditions.
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

{Standard polystyrene}
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

(Measurement of acid value)
The acid value was measured according to the JIS test method K 0070-1992. The acid value was determined by dissolving 0.5 g of a sample in tetrahydrofuran and titrating with a 0.1 M potassium hydroxide alcohol solution using phenolphthalein as an indicator.

(Measurement of solubility in water)
0.5 g of a polymer whose particle size was adjusted in the range of 250 μm to 90 μm using a sieve with a mesh size of 250 μm and 90 μm was sealed in a bag processed with a 400 mesh wire mesh, immersed in 50 mL of water, and 24 at a temperature of 25 ° C. The mixture was gently stirred for a long time. After soaking for 24 hours, the 400 mesh wire mesh containing the polymer was dried in a dryer set at 110 ° C. for 2 hours. The change in mass of the 400 mesh wire mesh containing the polymer before and after immersion in water was measured, and the solubility was calculated by the following formula.
Solubility [g / 100 mL] = (Polymer-encapsulated 400-mesh wire mesh [g] before immersion-Polymer-encapsulated 400-mesh wire mesh [g] after immersion) x 2

(Method of determining fine particle formation in water and method of measuring volume average particle size [nm])
(1) The acid value of the polymer was determined according to the method for measuring the acid value.
(2) After adding 1 g of the polymer to 50 mL of water, add a 0.1 mol / L potassium hydroxide aqueous solution that only neutralizes the acid value of the polymer obtained in (1) above to 100% neutralization. did.
(3) The 100% neutralized liquid is irradiated with ultrasonic waves at a temperature of 25 ° C. for 2 hours in an ultrasonic cleaner (ultrasonic cleaner US-102 manufactured by SND Co., Ltd., 38 kHz self-excited transmission). After being dispersed, it was left at room temperature for 24 hours.

A dynamic light scattering type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., a dynamic light scattering type particle size measuring device " Using the Microtrack particle size distribution meter UPA-ST150 "), the presence or absence of fine particle formation was confirmed from the light scattering information of the particles, and if the fine particles were present, the volume average particle diameter was measured.

(Measurement of static surface tension)
The static surface tension was measured with a Wilhelmj surface tension meter using the same sample liquid as the sample liquid obtained by the method for determining the formation of fine particles in water.

Table 1 shows the raw materials, reaction conditions, and various physical characteristic values of the polymer (P-1) obtained above. In Table 1, BuLi represents normal butyllithium, St represents styrene, α-MeSt represents α-methylstyrene, and tBMA represents tert-butylmethacrylate.

<Preparation of ink composition>
Cosmetic coloring materials (cosmetic pigments. Coloring material (B)) shown in Tables 2 and 3 below (150 g), polymer (P-1) (pigment dispersant (C)) 45 g, triethylene glycol (organic solvent (F)) ) 135 g and 20 g of a 34 mass% potassium hydroxide aqueous solution were charged into a 1.0 L intensive mixer (manufactured by Nippon Eirich Co., Ltd.) and kneaded at a rotor peripheral speed of 2.94 m / s and a pan peripheral speed of 1 m / s for 25 minutes. .. Subsequently, 450 g of ion-exchanged water was gradually added to the kneaded product in the container of the intensive mixer while continuing stirring, and then 200 g of ion-exchanged water was further added and mixed to obtain an aqueous pigment concentration of 15.0% by mass. A pigment dispersion was obtained.

AQUACER507 (binder resin, manufactured by BYK, polyolefin, average particle size 50 nm, melting point 130 ° C., non-volatile content 35% by mass) 17.14 g, triethylene glycol 0.6 g, distilled water in 40.00 g of the above-mentioned aqueous pigment dispersion. 20.36 g, 3-methoxy-1-butanol (manufactured by Daicel Co., Ltd.) 15.00 g, urea 5.0 g, triethanolamine 0.20 g, ACTICIDE MV4 (manufactured by So Japan Co., Ltd., preservative) 0.10 g, An ink composition was prepared by adding 1.60 g of SURFYNOL 104PG50 (acetylenedi alcohol-based surfactant manufactured by Air Products Co., Ltd.) and stirring the mixture.

<Evaluation of streaks on printed matter>
The above-mentioned ink composition is filled in the inkjet head KJ4B-YH manufactured by Kyocera Corporation, and the head difference of the ink sub-tank from the head nozzle plate surface is set to +35 cm and the negative pressure is set to -5.0 kPa to increase the supply pressure. It was adjusted. OPP film (Pyrene P2161, manufactured by Toyobo Co., Ltd., biaxially stretched polypropylene film) and PET film (Espet E5102, manufactured by Toyobo Co., Ltd., biaxially stretched polyester film) were prepared as the objects to be printed. The gap between the inkjet head and the corona-treated surface of the object to be printed was set to 1.2 mm. The drive conditions of the head are the standard voltage and standard temperature of the inkjet head, the droplet size is set to 18 pL, 100% density solid printing is performed on the printed matter, and then 1 in a warm air dryer at 60 ° C. A printed matter was obtained by drying the ink composition for minutes.

The printed matter was read by a scanner, and the ratio (streak ratio) of the portion where the ink composition was not applied was calculated by the image analysis software "ImageJ". The evaluation results based on the following criteria are shown in Tables 2 and 3.
A: Printed matter streak rate less than 10% B: Printed matter streak rate 10% or more and less than 20% C: Printed matter streak rate 20% or more

<Evaluation of settability of printed matter>
A printed matter was obtained by the same procedure as the above-mentioned streak evaluation. After taking out the printed matter from the warm air dryer, it was left at room temperature for 1 minute. Next, after superimposing the untreated corona-treated surface of the OPP film different from the above on the printed surface of the printed matter, a weight stone was set so as to have ^{a load of 100 g / cm 2, and the film was left for 1 minute.} After 1 minute, the weight was removed and the OPP film overlaid on the printed matter was peeled off. Then, the printed surface of the printed matter was read by a scanner, and the ratio (color residual ratio) of the area having the same color as that before stacking the OPP films to the printed area was analyzed by the image analysis software "ImageJ". The evaluation results based on the following criteria are shown in Tables 2 and 3.
A: Color residual rate of printed matter is 70% or more B: Color residual rate of printed matter is less than 70%

M1, M2, M3 ... T-shaped micromixer, P1, P2, P3, P4 ... tube reactor, R1, R2, R3 ... tube reactor.

Claims (4)

Contains an aqueous medium and a coloring material,
An inkjet ink composition, wherein the coloring material contains at least one selected from the group consisting of cosmetic pigments and cosmetic dyes. A method for producing a printed matter, comprising a step of obtaining a printed matter by printing the inkjet ink composition according to claim 1 by an inkjet recording method. The method for producing a printed matter according to claim 2, wherein the ink composition for inkjet is printed on a living body to obtain the printed matter. A method for producing a transfer sheet capable of transferring a printed matter on a substrate to an adherend.
A method for producing a transfer sheet, comprising a step of obtaining the printed matter on the substrate by the method for producing a printed matter according to claim 2.

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