JP2015134848A - colored resin particle dispersion and inkjet ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin particle dispersion and an inkjet ink which exhibit excellent abrasion resistance, and provide a colored resin particle dispersion and an inkjet ink which exhibit excellent abrasion resistance, together with excellent water resistance and marker resistance.SOLUTION: Provided is a colored resin particle dispersion containing colored resin particles, a basic dispersant, and a non-aqueous solvent, wherein the colored resin particles include a colorant, a solid resin and a liquid organic compound having an acidic group and a basic group. As the colorant, a phthalocyanine dye can be used.

Description

  The present invention relates to a colored resin particle dispersion and an inkjet ink.

  Color materials for printing ink are roughly classified into dyes and pigments. When using dye, there exists an advantage that coloring is good. Dyes have the advantage of being superior in abrasion resistance, particularly scratch resistance, compared to pigments. However, there is a problem that the water resistance and marker resistance of the dye itself are low.

  On the other hand, by including a dye in a resin to form colored resin particles, an ink having excellent water resistance and marker resistance as well as wear resistance is provided while taking advantage of the image property of the dye. There is a way. Here, it is desirable that the resin has characteristics that impart abrasion resistance, water resistance, and marker resistance to the ink.

  Patent Document 1, Patent Document 2 and Non-Patent Document 1 use an organic solvent A and an organic solvent B which is almost incompatible with the organic solvent A, and a dispersed phase and an organic material containing the organic solvent B and a resin. A polymer particle dispersion in which polymer particles are dispersed in the organic solvent A is prepared by removing the organic solvent B from the dispersion by reducing the pressure or heating, after preparing a dispersion composed of a continuous phase containing the solvent A. Has been proposed.

  That is, by dissolving and encapsulating a resin that does not dissolve in the organic solvent A in the organic solvent B and dispersing it in the organic solvent A to be a continuous phase, the organic solvent B is then removed by reducing or heating, It has been proposed to obtain a polymer particle dispersion in which polymer particles are stably dispersed in an organic solvent A.

  As the resin of the dispersed phase, a styrene-maleic acid copolymer resin is used in the example of Patent Document 1, a styrene-maleic acid copolymer resin and polyvinylpyrrolidone are used in the example of Patent Document 2, and in Non-Patent Document 1, Polyvinyl pyrrolidone is used. These resins are resins having a negatively dissociating polar group or resins having a positively dissociating polar group, and form a polymer particle having a negative charge or a positive charge to provide a stable dispersion. It has been proposed to be.

  In Patent Document 3, an organic solvent A and an organic solvent B that is hardly compatible with the organic solvent A are used, and a dispersed phase containing the organic solvent B and a polyfunctional monomer or resin and a polymerization initiator and the organic solvent A are used. A polymer in which polymer particles are dispersed in the organic solvent A by forming a dispersion liquid comprising a continuous phase and then causing a crosslinking reaction by light or heat and removing the organic solvent B from the dispersion liquid by reducing pressure or heating. It has been proposed to produce particle dispersions.

  According to the above documents, polymer particle dispersions are used as coloring materials for inks, copying toners, paints for various uses, liquid crystals to be colored, color filters for portable terminals, electronic books and electronic papers. It is desired that high-level to micro-level polymer particles are stably dispersed.

JP 2007-197632 A JP 2005-255911 A JP 2007-197633 A

Polymer Papers, Vol. 62, no. 7, pp. 310-315 (Jury, 2005)

  However, when adjusting printing inks using these polymer particle dispersions, the above literature does not discuss the abrasion resistance, water resistance, and marker resistance of images printed on paper or the like. It is difficult to obtain sufficient wear resistance of an image simply by adding a resin. In addition, there is a problem that it is difficult to maintain the stability of the dispersion when a resin that improves the abrasion resistance, water resistance, and marker resistance of the ink is used. Further, when a coloring material amount for obtaining a sufficient color developability of a printed image is blended, there is a problem that the viscosity of the polymer particle dispersion is increased and it becomes difficult to adjust the dispersion.

  In addition, the method of Patent Document 3 requires a polymerization reaction of a polyfunctional monomer or resin in the dispersed phase, and there is a problem that the number of production steps of the polymer particle dispersion is increased.

  An object of the present invention is to provide a colored resin particle dispersion and an inkjet ink that are excellent in wear resistance. Furthermore, it is providing the colored resin particle dispersion and inkjet ink which are excellent in water resistance and marker resistance with abrasion resistance.

  One aspect of the present invention includes colored resin particles, a basic dispersant, and a non-aqueous solvent, and the colored resin particles include a coloring material, a solid resin, and a liquid organic compound having an acidic group and a basic group. A colored resin particle dispersion.

  Another aspect of the present invention is an inkjet ink containing the above-described colored resin particle dispersion.

  According to the present invention, it is possible to provide a colored resin particle dispersion and ink excellent in wear resistance. Furthermore, it is possible to provide a colored resin particle dispersion and ink that are excellent in water resistance and marker resistance as well as abrasion resistance.

The colored resin particle dispersion according to an embodiment of the present invention (hereinafter sometimes simply referred to as “dispersion”) includes colored resin particles, a basic dispersant, and a non-aqueous solvent. And a solid resin and a liquid organic compound having an acidic group and a basic group (hereinafter sometimes simply referred to as “amphoteric compound”).
Thereby, it is possible to provide a colored resin particle dispersion and an ink excellent in wear resistance.

According to the present embodiment, since the amphoteric compound is contained in the colored resin particles, the coloring material and the solid resin are uniformly blended, and the abrasion resistance of the printed matter can be further improved. In particular, the scratch resistance can be increased.
In the production process of the colored resin particles, the amphoteric compound is blended in a solvent together with the colorant, particularly the phthalocyanine dye and the solid resin, and the system is stabilized, so that each component can be blended more uniformly. In particular, when producing a colored resin particle dispersion by an oil-in-oil emulsion, the emulsification stability of the emulsion is further improved by blending an amphoteric compound with a colorant and a solid resin in a solvent and using it as a dispersed phase. As a result, the components of the colored resin particles can be blended more uniformly.
Such an effect of wear resistance can be obtained regardless of the type of solid resin by including an amphoteric compound.

  In addition, since the color material is included in the solid resin, the marker resistance of the printed matter can be improved. When a printed material is traced with a marker, the printed material is rubbed by the marker, and in some cases, a solvent and ink contained in the marker may act. By including the color material in the solid resin, it is possible to further improve the solvent resistance as well as the scratch resistance. By including the amphoteric compound, the colorant and the solid resin are more uniformly and stably blended, so that the scratch resistance and solvent resistance can be further increased, and the marker resistance can be further increased.

  Even when a solid resin having water resistance is used as the solid resin, the colorant and the solid resin can be blended more uniformly and stably by including the amphoteric compound. Therefore, by using a solid resin having water resistance, it is possible to provide a colored resin particle dispersion having excellent water resistance as well as abrasion resistance of printed matter.

(Colored resin particles)
The colored resin particles according to the present embodiment include a color material, particularly a phthalocyanine dye, a solid resin, and an amphoteric compound.
The colored resin particles are preferably in the form of particles by uniformly mixing a coloring material, particularly a phthalocyanine dye, a solid resin and an amphoteric compound.

"Solid resin"
The solid resin is preferably a solid resin at room temperature (23 ° C.).
The glass transition temperature (Tg) of the solid resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize the particle shape. Although the glass transition temperature of solid resin is not restrict | limited, It is preferable that it is 150 degrees C or less, More preferably, it is 120 degrees C or less.
In addition, the melting temperature (Tm) of the solid resin is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, in order to stabilize the particle shape. The melting temperature of the solid resin is not limited, but is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.

  As a mass average molecular weight of solid resin, 3000-100,000 are preferable, More preferably, it is 5000-80000. Within this range, the stability of the shape of the colored resin particles can be enhanced. Moreover, in the manufacturing process of colored resin particles, the raw material containing a solid resin can be mixed uniformly with a solvent, and as a result, colored resin particles with uniform components can be provided.

  Here, the mass average molecular weight of the resin can be determined by standard polystyrene conversion by the GPC method. The same applies hereinafter.

The solid resin preferably has a Hansen solubility parameter (HSP value) of 22 to 27 MPa / cm ³ . The solid resin preferably has a dispersion term δd of 13 to 20, a polar term δp of 5 to 12, and a hydrogen bond term δh of 10 to 20. By setting it as this range, when the ink as the colored resin particle dispersion is applied to the paper, the colored resin particles and the non-aqueous solvent can be quickly separated, and the wear resistance can be further improved.

A method for calculating the solubility parameter will be described below. In the present invention, the three-dimensional solubility parameter proposed by Hansen in 1967 is used.
Hansen's solubility parameter is obtained by dividing the solubility parameter introduced by Hildebrand into three components of a dispersion term δd, a polar term δp, and a hydrogen bond term δh, and is expressed in a three-dimensional space. The dispersion term indicates the effect due to the dispersion force, the polarity term indicates the effect due to the force between the dipoles, and the hydrogen bond term indicates the effect due to the hydrogen bond force. More specifically, POLYMER HANDBOOK. FOURTH EDITION. (Editors. J. BRANDRUP, E. H. IMMERGUT, and E. A. GRULKE.) And the like.

The Hansen solubility parameter can be determined experimentally as described below.
First, the solubility (10 mass%) of an object (solid resin or the like) is investigated with respect to the solvents shown in Table 1 whose dispersion term δd, polar term δp, and hydrogen bond term δh are known. Next, the range (minimum value and maximum value) of the dispersion term δd, the polar term δp, and the hydrogen bond term δh corresponding to the range of the solvent in which the object is dissolved is obtained, and an intermediate value (of the range of the three-dimensional solubility parameter) The center value) is taken as the three-dimensional solubility parameter of the object. That is, considering the largest rectangular parallelepiped in which the good solvent is inside and the poor solvent is outside, the center of the rectangular parallelepiped is determined as the solubility parameter (HSP value) of the object.

Dispersion term δd = (δd _max −δd _min ) / 2
Polarity term δp = (δp _max −δp _min ) / 2
Hydrogen bond term δh = (δh _max −δh _min ) / 2
HSP ² = δd ² + δp ² + δh ²

  It is preferable to select a solvent used in the solubility test that is located in a three-dimensional space with different solubility parameters (HSP values). Table 1 shows the solubility parameter (HSP value), dispersion term δd, polar term δp, and hydrogen bond term δh of each solvent.

As the solid resin, those having the above physical properties can be preferably used, and the kind thereof is not limited.
Specific examples of the solid resin include alkylphenol resin, polyvinyl alcohol (PVA), (meth) acrylic resin, styrene (meth) acrylic resin, styrene maleic acid resin, cellulose resin, polyvinyl acetal resin, methoxymethylated nylon, etc. Polyamide resin, ketone resin, rosin resin, vinyl acetate, polyvinylpyrrolidone, phosphate esterified solid resin, nitrate esterified solid resin, alkoxy group-containing solid resin, polysilsesquioxane, methoxysilsesquioxane, ethoxysilsesquito Oxane, derivatives of these resins, and the like can be given.
These can be used alone or in combination of two or more.
The (meth) acrylic resin means a methacrylic resin and / or an acrylic resin, and means a copolymer having both a methacrylic unit and an acrylic unit together with a polymer having a methacrylic unit and an acrylic unit alone. To do. The same applies to styrene (meth) acrylic resins.

  Polyvinyl alcohol is generally a resin that contains polyvinyl acetate as a raw material and is substituted with an acetate group together with a hydroxyl group, depending on the ratio of substitution. .

When the molar ratio of units having a hydroxy group is n and the molar ratio of units having an acetic acid group (—O—CO—CH ₃ ) is m with respect to all units constituting the polyvinyl alcohol, the saponification degree is n / (N + m) × 100, the degree of polymerization is represented by n + m.

  The degree of saponification of polyvinyl alcohol (n / (n + m)) × 100 is preferably 0 to 60, and more preferably 1 to 50.

  As a polymerization degree (n + m) of polyvinyl alcohol, it is preferable that it is 10-1000, More preferably, it is 20-500.

  As a polyvinyl acetal resin, what is manufactured by acetalizing polyvinyl alcohol (PVA) resin can be used. Specifically, a polyvinyl acetal resin can be produced by reacting a PVA resin with an aldehyde with an acid catalyst to acetalize part or all of the hydroxyl groups of the PVA resin.

  The saponification degree (n / (n + m) × 100) of polyvinyl alcohol necessary for preparing the polyvinyl acetal resin is preferably 2 or more, more preferably 5 or more. This proportion of hydroxy groups is suitable for acetalization.

  Moreover, as a polymerization degree (n + m) of polyvinyl alcohol, it is preferable that it is 10-1000, More preferably, it is 20-500.

  As an aldehyde, formaldehyde, acetaldehyde, paraformaldehyde, trioxane, tetraoxane, propionaldehyde, butyraldehyde, etc. can be used as an example.

As the aldehyde, alicyclic aldehydes and aromatic aldehydes can be used.
Examples of the alicyclic aldehydes include cyclohexane carboxaldehyde, 5-norbornene-2-carboxaldehyde, 3-cyclohexene-1-carboxaldehyde, dimethyl-3-cyclohexene-1-carboxaldehyde, and the like.
Aromatic aldehydes include 2,4,6-trimethylbenzaldehyde (mesitaldehyde), 2,4,6-triethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 2-methylbenzaldehyde, 2-methoxy-1-naphthaldehyde 2-ethoxy-1-naphthaldehyde, 2-propoxy-1-naphthaldehyde, 2-methyl-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, other 1-naphthaldehyde having a substituent, Examples thereof include 2-naphthaldehyde having, 9-anthraldehyde, 9-anthraldehyde having a substituent, and the like.

In addition to or in place of the aldehyde, a ketone may be used.
Examples of the ketone include acetophenones such as 2-methylacetophenone and 2,4-dimethylacetophenone, and naphthones such as 2-hydroxy-1-acetonaphthone, 8′-hydroxy-1′-benzonaphthone and acetonaphthone.
These aldehydes and ketones may be used alone or in combination.

  The polyvinyl acetal resin preferably has an acetalization degree of 40 to 95 mol%, more preferably 50 to 85 mol%. Thus, when the solid resin is mixed with the coloring material and the solvent in the manufacturing process of the colored resin particles, the solubility of the solid resin in the solvent can be improved. As a result, the uniformity of the components of the colored resin particles and the stability of the shape can be enhanced.

  The degree of acetalization of the polyvinyl acetal resin can be expressed as the ratio of the acetalized hydroxyl group among the hydroxyl groups of the polyvinyl alcohol resin. In the case of polyvinyl butyral resin, it can be measured according to JISK6728.

  As for the degree of acetalization, the ratio of polyvinyl alcohol resin acetalized with butyraldehyde is sometimes referred to as the degree of butyralization. This degree of butyralization is preferably in the same range as the above-mentioned degree of acetalization.

  The polyvinyl acetal resin preferably has a hydroxyl group of 60 mol% or less, more preferably 50 mol% or less. Thus, when the solid resin is mixed with the coloring material and the solvent in the manufacturing process of the colored resin particles, the solubility of the solid resin in the solvent can be improved. As a result, the uniformity of the components of the colored resin particles and the stability of the shape can be enhanced.

  Here, the ratio of the hydroxyl group of the solid resin can be expressed as the ratio of the unit (mol) having a hydroxyl group to the total unit (mol) constituting the solid resin. The same applies hereinafter.

  As the polyvinyl acetal resin, a polyvinyl butyral resin obtained by acetalizing a polyvinyl alcohol resin with butyraldehyde (hereinafter sometimes referred to simply as a butyral resin), a polyvinyl formal resin obtained by acetalizing a polyvinyl alcohol resin with formaldehyde ( Vinylon) can be preferably used.

As a commercial item of polyvinyl butyral resin, for example, S-LEC B series “BL-2H”, “BL-10”, “BL-S”, “BM-1”, “BM-2” manufactured by Sekisui Chemical Co., Ltd. , “MN-6”, “BX-L”, etc .; Kuraray Co., Ltd.'s Mobital B series “16H”, “20H”, “30T”, “30H”, “30HH”, “45M”, “45H” and the like can be used.
As a commercial item of polyvinyl formal resin, for example, vinylec series “Vinylec K”, “Vinylec C” manufactured by JNC Corporation; vinylon fiber manufactured by Kuraray Co., Ltd., or the like can be used.
These may be used alone or in combination of two or more.

The alkylphenol resin may be either a novolak type alkylphenol resin or a resol type alkylphenol resin, or may be used in combination.
The novolak type alkylphenol resin can be produced by reacting an alkylphenol and an aldehyde in the presence of an acid catalyst.
The resol type alkylphenol resin can be produced by reacting an alkylphenol and an aldehyde in the presence of an alkali catalyst.
A modified alkylphenol resin may also be used. Examples of the modified alkylphenol resin include rosin-modified alkylphenol resin and alkoxy group-containing silane-modified alkylphenol resin.

  The alkylphenol as a raw material preferably has an alkyl group having 1 to 12 carbon atoms. Examples of alkylphenols include o-cresol, m-cresol, p-cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, octylphenol, nonylphenol, dodecylphenol, bisphenol A, bisphenol B, bisphenol C, and bisphenol E. Bisphenol F or the like can be used. These may be used alone or in combination of two or more. In addition, the position of the substituent of these alkylphenols is not limited.

  As an aldehyde, for example, formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde, trioxane, tetraoxane, or a combination thereof can be used.

  Examples of the cellulose resin include cellulose acetate resin, cellulose acetate butyrate resin, cellulose acetate propionate resin, and nitrocellulose.

  As the (meth) acrylic resin, in addition to the (meth) acrylic resin having a methacrylic unit and / or an acrylic unit, a copolymer having another unit together with the methacrylic unit and / or the acrylic unit can be used. Other units include styrene units, vinyl carboxylate units, α-olefin units, diene units, ethylenically unsaturated acid units, ethylenically unsaturated acid anhydride units, monoalkyl ester units of unsaturated carboxylic acids, Examples thereof include sulfonic acid units, nitrogen-containing units such as nitrile, pyridine, and pyrrolidone, and ether-based units.

  The (meth) acrylic resin can be obtained by polymerization of a known (meth) acrylic monomer. (Meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic N-butyl acid, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, (meth ) Isooctyl acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate , Octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, pheny (meth) acrylate , (Meth) acrylic acid alkyl ester, (meth) acrylic acid 2-hydroxyester, (meth) acrylic acid 2-hydroxypropyl, (Meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl etc. ) Hydroxyalkyl ester of acrylic acid, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol poly Mono (meth) of polyalkylene glycols (the number of alkylene glycol units is 2 or more) such as tylene glycol mono (meth) acrylate, polypropylene glycol polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol polybutylene glycol mono (meth) acrylate, etc. Acrylate: Methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, methoxypolybutylene glycol mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, ethoxypoly Alkoxypolyalkylene such as butylene glycol mono (meth) acrylate Esters of (meth) acrylic acid containing a polyalkylene oxide skeleton such as mono (meth) acrylic acid ester of glycol, (meth) acrylamide, dimethylaminoethyl (meth) acrylate, N-butoxymethylacrylamide, N, N-dimethylacrylamide Nitrogen-containing monomers such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, epoxy group-containing (meth) acrylic acid such as 3,4-epoxycyclohexylmethyl (meth) acrylate, sulfoethyl acrylate, (meth) Examples thereof include unsaturated sulfonic acids such as acryloxybenzene sulfonic acid, and two or more of these may be used in combination.

  In addition, monomers other than (meth) acrylic monomers (hereinafter referred to as other monomers) can be used in combination. Other monomers are not particularly limited as long as they can be copolymerized with (meth) acrylic monomers. For example, styrene monomers such as styrene and α-methylstyrene, vinyl acetate, vinyl propionate, and the like. Carboxylic acid vinyl ester such as ethylene, propylene, butene-1, etc., diene monomer such as butadiene, isoprene, crotonic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride Such as ethylenically unsaturated acids and anhydrides thereof, maleic acid monoesters, fumaric acid monoesters, monoalkyl esters of unsaturated carboxylic acids such as itaconic acid monoesters, (meth) acrylonitrile, vinylpyridine, vinylpyrrolidone, etc. Nitrogen-containing unsaturated monomer, (meth) allylsulfonic acid, vinylsulfonic acid, p-styrenesulfonic acid, 2 -Unsaturated sulfonic acid such as acrylamido-2-methylpropane sulfonic acid, vinyl ether monomers such as vinyl ethyl ether, vinyl isobutyl ether and vinyl phenyl ether, and the like may be used in combination of two or more.

As the (meth) acrylic resin, the number average molecular weight (Mn) is preferably 5000 to 25000, the acid value is preferably 0 to 300 mgKOH / g, and more preferably 30 to 300 mgKOH / g. preferable.
A (meth) acrylic resin having a styrene unit can be preferably used as a styrene (meth) acrylic resin. In this case, the ratio (molar ratio) between the styrene unit and the (meth) acryl unit is preferably from 0:10 to 7: 3.

  Examples of commercially available (meth) acrylic resins include “UC-3000” of ARUFON series manufactured by Toa Gosei Co., Ltd .; “TS-1315”, “RS-1190” of Hyros X series manufactured by Seiko PMC Co., Ltd., styrene ( Commercially available products of (meth) acrylic resins include “UC-3920” and “UC-5041” of ARUFON series manufactured by Toa Gosei Co., Ltd .; “VS-1047” and “VS-1291” of Hyros X series manufactured by Seiko PMC Co., Ltd. Or the like.

  The styrene maleic acid resin is a copolymer of styrene and maleic anhydride. As the styrene maleic resin, an esterified product obtained by esterifying a styrene maleic resin and introducing a carboxy group or a hydroxy group can be used.

  Examples of commercially available styrene maleic acid resins and esterified products thereof include styrene maleic resin such as SMA resin series “SMA1440F”, “SMA1440”, “SMA17352”, “SMA2625”, “SMA3840” manufactured by Kawa Crude Chemical Co., Ltd. Styrene maleic resin such as SMA resin series “SMA1000”, “SMA2000”, “SMA3000” manufactured by Kawa Crude Chemical Co., Ltd. can be used.

  As the polyamide resin, nylon-6, nylon-66, nylon 4-6, copolymer nylon, or the like can be used.

Moreover, the polyamide resin which has the alkoxy group which alkoxymethylated the polyamide resin can be used.
By subjecting the polyamide resin to alkoxymethylation, the solubility in an alcohol solvent can be increased. Therefore, in the resin particle manufacturing process, the color material and the resin component can be more uniformly and stably mixed in the solvent.
Examples of the alkoxymethyl group include a methoxymethyl group and an ethoxymethyl group.

Examples of commercially available polyamide resins include the tomide series manufactured by T & K TOKA Corporation, PA series, and fine resin series "FR-101", "FR-104", "FR-105" manufactured by Lead Corporation. Examples include “FR-301” and other resin series “TRESIN F-30K” and “TORESIN EF-30T” manufactured by Nagase ChemteX Corporation.

  By using a nitrogen-containing resin as the solid resin, it is possible to improve the dispersibility of the pigment that is a coloring material when producing colored resin particles. Accordingly, colored resin particles can be produced using only a nitrogen-containing resin and without using a pigment dispersant. As the nitrogen-containing resin, polyamide resins such as nitrocellulose and methoxymethylated nylon can be preferably used from the above.

  In addition, by using an aromatic ring-containing resin as the solid resin, a π-π interaction between the pigment that is a coloring material and the aromatic ring-containing resin can be expected, so that the dispersibility of the pigment can be improved. As the aromatic ring-containing resin, styrene resins such as styrene (meth) acrylic resin and styrene maleic acid resin can be preferably used from the above.

The blending amount of the solid resin is preferably 10% by mass or more, more preferably 20% by mass or more, based on the entire colored resin particles.
On the other hand, it is preferable that the compounding quantity of solid resin is 70 mass% or less with respect to the whole colored resin particle, More preferably, it is 50 mass% or less.

  The colored resin particles may contain other resins other than the above-described resins as long as the effects of the present invention are not impaired. Other resins include additives as described in the method for producing a colored resin particle dispersion described later.

"Coloring material"
The color material contained in the colored resin particles may be either a pigment or a dye, or a combination thereof. A dye is preferred.

  As the dye, those generally used in the technical field can be arbitrarily used. For example, basic dye, acid dye, direct dye, soluble vat dye, acid mordant dye, mordant dye, reactive dye, vat Examples thereof include dyes, sulfur dyes, metal complex dyes, and salt-forming dyes. You may use these individually or in combination of multiple types.

  Specific examples of the dye include azo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoneimine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes. Dyes, phthalocyanine dyes, metal phthalocyanine dyes, triarylmethane dyes, rhodamine dyes, sulforhodamine dyes, methine dyes, azomethine dyes, quinone dyes, phthalocyanine dyes, triphenylmethane dyes, diphenylmethane dyes, methylene blue, etc. it can. These may be used alone or in combination of two or more.

  Preferably, the dye has higher solubility in the solvent B than in the solvent A, so that the resin is dissolved in the solvent B together with the dye in the dispersed phase, so that the colored resin particle dispersion can be stably provided.

  Here, the solubility of the dye in the solvent B is preferably 0.5 g / 100 g or more at 23 ° C., more preferably 1 g / 100 g or more. More preferably, the dye is selected such that substantially all of the dye is dissolved in the solvent B at the blending ratio of the oil-in-oil emulsion.

  The dye is preferably an oil-soluble dye from the viewpoint of water resistance of the colored resin particles. Moreover, by using an acidic dye, a basic dispersant is contained in the continuous phase and an acidic acidic dye is contained in the dispersed phase, so that the oil-in-oil emulsion can be further stabilized. Preferred are phthalocyanine dyes and metal complex dyes. For example, phthalocyanine dyes having a central metal can be preferably used.

  The phthalocyanine dye is a dye having a phthalocyanine skeleton. The phthalocyanine skeleton is represented by the following chemical formula (1).

  The phthalocyanine dye may have a central metal at the center of the phthalocyanine skeleton represented by the chemical formula (1) and may have an arbitrary substituent.

Examples of the central metal of the phthalocyanine skeleton include copper, cobalt, nickel, zinc, chromium, and iron. In addition, phthalocyanine in which the central hydrogen is unsubstituted may be used.
Among these, copper phthalocyanine can be preferably used.

Also, phthalocyanine dyes include sulfonated copper phthalocyanine, amine salt or ammonium salt of sulfonated copper phthalocyanine, phthalimide copper phthalocyanine, chloromethylated phthalocyanine, nitrated copper phthalocyanine, chlorinated phthalocyanine, brominated phthalocyanine, chlorinated sulfonation Phthalocyanine derivatives such as halogenated sulfonated phthalocyanines such as phthalocyanine and brominated sulfonated phthalocyanine, and amine salts or ammonium salts of halogenated sulfonated phthalocyanines can be used.
Among these, sulfonated copper phthalocyanine, its amine salt or ammonium salt can be preferably used.
Moreover, a phthalocyanine having a sulfonamide group introduced by reacting a halogenated sulfonated copper phthalosinin with an aliphatic amine or the like can be preferably used.
Specific examples include disulfonated copper phthalocyanine amine salt, copper phthalocyanine tetrasulfonate sodium, copper phthalocyanine trisulfonate sodium, copper phthalocyanine disulfonate sodium, and copper phthalocyanine monosulfonate sodium.
These can be used alone or in combination of two or more.

Examples of the phthalocyanine dye include C.I. I. Solvent Blue 25, 38, 44, 70, 55 etc., C.I. I. Direct blue 87, 86, 199, etc., CI acid blue 249, 249, etc. can be mentioned.
These can be used alone or in combination of two or more.

Examples of commercially available phthalocyanine dyes include “Valifast Blue” series 1605 (solvent blue 38), 1621 (direct blue 87), 2620 (solvent blue 44), and 2670 (solvent blue 70) manufactured by Orient Chemical Industries, Ltd. , 2606 (solvent blue 70), etc.
650 (Solvent Blue 70) of “Oil Blue” series manufactured by Orient Chemical Co., Ltd.
“DaiwaIJ Blue 319H” (Direct Blue 199) manufactured by Daiwa Kasei Co., Ltd.
Examples include “SPT BLUE 121” and “Spilon Blue GHN” manufactured by Hodogaya Chemical Co., Ltd.
These can be used alone or in combination of two or more.

  The phthalocyanine dye is preferably blended in an amount of 0.1 to 50% by mass, more preferably 1 to 40% by mass with respect to the entire colored resin particles, from the viewpoint of colorability and component uniformity. .

  As other oil-soluble dyes, for example, OILBlue 613, OILYellow 107, SpiritBlackAB, ROB-B, etc. of “OIL COLOR series” manufactured by Orient Chemical Industry Co., Ltd. can be used.

Other metal complex dyes include, for example, “VALIFAST COLOR series” manufactured by Orient Chemical Industry Co., Ltd., Valifast Black 3804, 3810 (Solvent Black 29), 3820, 3830, 3840 (Solvant Black 27), 3870, VariFast Orange 3209, 3210, ValifNastPink 23, 2312, VariFastRed 3304, 3311, 3312, 3320, Varifast Yellow 3108, 3170, 4120, 4121, etc .;
BASF's “ORAZOL Series” Orazole Black RLI, Blue GN, Pink 5BLG, Yellow 2RLN, etc .;
Eisenspiron BlackBH, RLH, Eisenspiron VioletRH, Eisenspiron RedCBH, BEH, Eisenspiron YellowGRH, Eisen SPPTBlue26, Eisen SPPTBlue121, Eisen SPTBlue510, etc. can be used. .

  As the pigment, organic pigments such as azo pigments, phthalocyanine pigments, polycyclic pigments, dyed lake pigments, and inorganic pigments such as carbon black and metal oxides can be used. Examples of the azo pigments include soluble azo lake pigments, insoluble azo pigments, and condensed azo pigments. Examples of phthalocyanine pigments include metal phthalocyanine pigments and metal-free phthalocyanine pigments. Polycyclic pigments include quinacridone pigments, perylene pigments, perinone pigments, isoindoline pigments, isoindolinone pigments, dioxysazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments. And diketopyrrolopyrrole (DPP). Examples of carbon black include furnace carbon black, lamp black, acetylene black, and channel black. Examples of the metal oxide include titanium oxide and zinc oxide. These pigments may be used alone or in combination of two or more.

In the case of using a pigment for the color material, a pigment dispersant may be included in the dispersed phase in order to disperse the pigment more stably in the solvent in the dispersion manufacturing process described later.
As the pigment dispersant, any of an anionic dispersant, a cationic dispersant, and a nonionic dispersant may be used, and may be appropriately selected depending on other components.

  In the case of using a pigment for the color material, a solid chip in which the pigment is dispersed in advance in the above-described solid resin can be used. In this case, the affinity between the pigment and the resin can be improved, and the wear resistance can be further improved, and it is also advantageous for ink production. As a method for dispersing the pigment in the solid resin, a two-roll mill or the like can be used.

  The coloring material is preferably blended in an amount of 0.1 to 50% by mass, more preferably 1%, from the viewpoint of colorability and component uniformity, with respect to the entire colored resin particles, as the total amount of dye and pigment. -40 mass%.

"Liquid organic compounds having acidic and basic groups"
The colored resin particles include a liquid organic compound (an amphoteric compound) having an acidic group and a basic group.
Wear resistance can be improved by adding amphoteric compounds. This is because the amphoteric compound makes it possible to blend a color material, particularly a phthalocyanine dye and a solid resin, more uniformly and stably.
In addition, when a resin with a low acid value and high water resistance is used as the solid resin, the wear resistance may be reduced. By adding an amphoteric compound together with this solid resin, the water resistance and the wear resistance are improved. Can be made.

Moreover, the amphoteric compound can further improve the stability of the oil-in-oil emulsion in the production process of the colored resin particle dispersion.
When the amphoteric compound has an acidic group and a basic group, the compatibility with the coloring material can be improved, and the solubility of each component in the lower alcohol solvent can be increased. Thereby, this dispersed phase can be stably dispersed in the continuous phase.

This amphoteric compound is liquid at room temperature (23 ° C.) and preferably has 2 or more carbon atoms.
The melting point of the amphoteric compound is preferably 23 ° C. or lower, more preferably 15 ° C. or lower in order to maintain a liquid state at room temperature.

As the solubility parameter of the amphoteric compound, the Hansen solubility parameter (HSP value) is preferably 22 to 27 MPa / cm ³ . The amphoteric compound preferably has a dispersion term δd of 13 to 20, a polar term δp of 5 to 12, and a hydrogen bond term δh of 10 to 20. By setting it within this range, each component of the colored resin particles can be blended more uniformly, the particle shape can be stabilized and the stability over time can be further improved, and the coloring property and wear resistance can be improved. It can be improved further.

  Examples of the acidic group of the amphoteric compound include a phosphate group, a carboxy group, a sulfonic acid group, a phosphate ester group, a sulfate ester group, a nitrate ester group, a phosphorous acid group, a phosphonic acid group, and a sulfinic acid group. . These may be contained in one molecule or in combination of two or more.

  Examples of the basic group of the amphoteric compound include an amino group and a pyridyl group, and among these, an amino group is preferable. Examples of the basic group of the amphoteric compound include a nitrogen-containing functional group having a urethane bond, an amide bond, or the like. Moreover, you may introduce | transduce into the amphoteric compound as a nitrogen-containing structural unit which has a urethane bond, an amide bond, etc. These may be contained in one molecule or in combination of two or more.

The amphoteric compound may be an oligomer, a polymer, or a low molecular weight compound.
As the oligomer or polymer, for example, poly (meth) acrylic resin, polyester resin, polyvinyl resin, polyether resin, styrene-maleic acid copolymer resin, polyurethane resin, etc. may be used alone or in combination. Can be used. Moreover, you may use the copolymer of the monomer or oligomer which comprises these resin.

  As the liquid organic compound having an acidic group and a basic group, for example, an amine salt or alkylammonium salt of an oligomer or polymer having an acidic group can be used.

  Moreover, as a liquid organic compound which has an acidic group and a basic group, the phosphate ester salt of the oligomer or polymer which has a basic group, etc. can be used, for example.

  Moreover, as a liquid organic compound which has an acidic group and a basic group, what modified | denatured the oligomer or the polymer and introduce | transduced the acidic group and the basic group can be used, for example. For example, a modified (meth) acrylic block copolymer can be mentioned.

  Moreover, as a liquid organic compound which has an acidic group and a basic group, the salt of the monomer, oligomer, or polymer which has an acidic group, and the monomer, oligomer or polymer which has a basic group can be used, for example. For example, a salt of a long-chain polyaminoamide and a polyester having an acidic group can be mentioned.

  When the amphoteric compound is an oligomer or a polymer, the mass average molecular weight is preferably 500 to 10,000, more preferably 1,000 to 5,000.

  The amphoteric compound preferably has an acid value. The acid value of the amphoteric compound is preferably 10 KOH mg / g or more, more preferably 20 KOH mg / g or more, and still more preferably 30 KOH mg / g or more.

  The amphoteric compound preferably has a base number. The base value of the amphoteric compound is preferably 10 KOH mg / g or more, more preferably 20 KOH mg / g or more, and still more preferably 30 KOH mg / g or more.

  Here, the acid value is the number of milligrams of potassium hydroxide necessary to neutralize all acidic components in 1 g of the nonvolatile content, and the base value neutralizes all basic components contained in 1 g of the nonvolatile content. Is the number of milligrams of potassium hydroxide equivalent to the hydrochloric acid required for the reaction. The same applies hereinafter.

  The amphoteric compound preferably has an acid value of 10 KOH mg / g or more and a base value of 10 KOH mg / g or more, more preferably an acid value of 30 KOH mg / g or more and a base value of 30 KOH mg. More preferably, the acid value is 90 KOHmg / g or more, and the base value is 90 KOHmg / g or more. The acid value / base value is preferably 0.3 to 3.0, more preferably 0.5 to 2.0.

  Moreover, as an ORP value when the liquid organic compound which has an acidic group and a basic group is dissolved 5 mass% in methanol, it is more preferable that it is 0 or more and less than 200 mV.

  Here, the oxidation-reduction potential (ORP value) was measured by inserting a working electrode and a reference electrode into solutions of various materials at a measurement temperature of 23 ° C. using a silver electrode as a working electrode and a silver chloride electrode as a reference electrode. It is. For example, the oxidation-reduction potential can be measured using an ORP electrode “ORP-14” (both manufactured by FUSO Corporation) on a portable pH meter “pH-208”.

Among the commercially available products, those that can be used as the liquid organic compound having an acidic group and a basic group include, for example, “DISPERBYK-145, 180, 191, 9076, 106, 187, manufactured by Big Chemie Japan Co., Ltd. 142, 2020, etc. ”“ ANTI-TERRA-U, U 100, 204, 205, etc. ”(all trade names);
“Solsperse 24000SC, 24000GR, 32000, 33000, 39000, etc.” manufactured by Nippon Lubrizol Corporation;
Ajinomoto Fine Techno Co., Ltd. "Ajisper PB821, 822, 881 etc." can be mentioned.

“DISPERBYK-145” is a phosphate ester salt of a copolymer having an acid value of 76 KOH mg / g and a base value of 71 KOH mg / g and having a basic group.
“DISPERBYK-180” is an alkyl ammonium salt of a copolymer having an acid value of 94 KOH mg / g, a base value of 94 KOH mg / g, and having a phosphate group as an acidic group.
“DISPERBYK-191” is an amphoteric acetate copolymer having an acid value of 30 KOH mg / g and a base value of 20 KOH mg / g, having an amine group and a carboxylic acid group, and is a polyacrylic resin.
“DISPERBYK-9076” has an acid value of 38 KOH mg / g and a base value of 44 KOH mg / g, and is an alkylammonium salt of a high molecular weight copolymer.

  The amphoteric compound is preferably blended in an amount of 0.1 to 50 mass%, more preferably 1 to 40 mass%, based on the entire colored resin particles. Thereby, while maintaining the uniformity and stability of the components of the colored resin particles, the action on other raw materials can be prevented.

"Plasticizer"
In addition to the acidic compound described above, the colored resin particles can further contain a liquid organic compound (hereinafter, simply referred to as “plasticizer”) that does not have an acidic group. Thereby, the abrasion resistance of the printed material can be further improved.
The plasticizer lowers the softened region of the solid resin to give plasticity, and when the solid resin and the color material of the colored resin particles are mixed, the plasticizer is blended so that the solid resin and the color material described above are mixed. It is possible to mix more uniformly. Thereby, the components of the colored resin particles become uniform, and the wear resistance can be further improved.

The solubility of the plasticizer in the non-aqueous solvent is preferably 3 g / 100 g or less at 23 ° C., and imparts plasticity to the solid resin of the colored resin particles and prevents dissolution in the non-aqueous solvent. Stability can be maintained. Moreover, when manufacturing a colored resin particle dispersion, coalescence of the dispersed phase containing a solid resin and a coloring material can be prevented, and the stability of the oil-in-oil emulsion can be further enhanced. As a result, the components of the colored resin particles can be made more uniform.
This solubility is more preferably 1 g / 100 g or less at 23 ° C., and still more preferably 0.5 g / 100 g or less. Most preferably, in the blending ratio of the colored resin particle dispersion, the plasticizer does not substantially dissolve in the non-aqueous solvent.

  The melting point of the plasticizer is preferably 23 ° C. or lower, more preferably 15 ° C. or lower. Thereby, the solid resin and the color material of the colored resin particles can be mixed more uniformly.

  As a plasticizer, any of a low molecular weight compound, a high molecular compound, and these combination may be sufficient.

  As the low molecular weight compound, for example, alcohols, esters, ethers and the like can be used.

  As alcohols, lower polyhydric alcohols and / or higher polyhydric alcohols can be preferably used. The number of hydroxy groups in the alcohol is preferably 1-10.

The carbon number of the lower polyhydric alcohol is preferably 4-6.
Specific examples of the lower polyhydric alcohol include diols such as 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol.

The carbon number of the higher polyhydric alcohol is preferably 10 to 250.
Specific examples of the higher polyhydric alcohol include polyols such as castor oil polyol.

As the esters, low molecular esters can be preferably used.
The carbon number of the low molecular ester is preferably 8-30.
Specific examples of the low molecular ester include diisononyl phthalate, di-2-ethylhexyl adipate, diisononyl adipate, and the like.

As the plasticizer, polymer compounds such as polyesters, polyethers, and (meth) acrylic polymers can be preferably used.
As a mass mean molecular weight of a high molecular compound, it is preferable that it is 300-8000, More preferably, it is 1000-5000. As a result, the shape stability and plasticity of the colored resin particles can be provided in a well-balanced manner.

Examples of polyesters include polyester polyols obtained by esterification reaction of low molecular weight polyols and dibasic acids, polycaprolactone, poly-β-methyl-δ-valerolactone, and the like.
Examples of the polyester polyol include diethylene glycol adipate (AA-DEG), neopentyl glycol adipate (AA-NPG), and trimethylolpropane adipate / diethylene glycol (AA-TMP / DEG).

  Examples of polyethers include polyether polyols such as polyethylene glycol, polyoxypropylene glycol, and poly (oxytetramethylene) glycol.

  As (meth) acrylic polymers, in addition to (meth) acrylic resins having methacrylic units and / or acrylic units, copolymers having other units together with methacrylic units and / or acrylic units can be used. Examples of other monomers that can be used include vinyl acetate units and styrene units.

Examples of commercially available (meth) acrylic polymers include “ARUFONUP-1010”, “ARUFONUP-1190”, “ARUFONUH-2000”, “ARUFONUH-2190”, “ARUFONUH-2041”, “ARUFONUG-4010” manufactured by Toa Gosei Co., Ltd. ”,“ ARUFONUS-6100 ”and the like.
These plasticizers may be used alone or in combination of two or more.
Among these, polyesters, polyethers, and (meth) acrylic polymers can be preferably used alone or in combination.

  The amount of the plasticizer described above is preferably 5% by mass to 40% by mass with respect to the entire colored resin particles.

The average particle diameter of the colored resin particles is preferably about 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. Depending on the type of the recording medium, the average particle diameter of the colored resin particles may be adjusted as appropriate.For example, in order to improve the color development of a printed material using coated paper and improve the fixability, the average particle diameter is The thickness is preferably about 100 to 250 nm, and further preferably 140 to 250 nm from the viewpoint of suppressing the back-through of printed matter using plain paper.
Here, the average particle size of the colored resin particles is a volume-based average particle size by a dynamic scattering method, such as a dynamic light scattering type particle size distribution measuring device “LB-500” manufactured by Horiba, Ltd. Can be measured. The same applies hereinafter.

(Colored resin particle dispersion)
The colored resin particle dispersion according to the present embodiment includes a non-aqueous solvent and a basic dispersant together with the above-described colored resin particles. About a non-aqueous solvent and a basic dispersing agent, it is as explaining with the manufacturing method of the below-mentioned colored resin particle dispersion. The non-aqueous solvent is preferably a solvent that can disperse the colored resin particles. The basic dispersant is blended to disperse the colored resin particles in a non-aqueous solvent. Moreover, a basic dispersant may be mix | blended for adjustment of an emulsion in the manufacturing process of the colored resin particle mentioned later.

  From the viewpoint of dispersibility, the basic dispersant is preferably blended in an amount of 0.1 to 20% by mass, more preferably 1 to 15% by mass, based on the entire dispersion.

In the colored resin dispersion according to this embodiment, the colored resin particles are preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more based on the entire dispersion. As a result, the ink has excellent color developability, and the amount of solvent can be reduced to increase the drying property.
On the other hand, the colored resin particles are preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less based on the entire dispersion. Thereby, dispersibility and storage stability can be improved.

(Method for producing colored resin particle dispersion)
Hereinafter, an example of the manufacturing method of the colored resin particle dispersion according to the present embodiment will be described. In addition, the colored resin particle dispersion according to the present embodiment is not limited to those manufactured by the following manufacturing method.

  Methods for adjusting the colored resin particle dispersion are roughly classified into chemical methods and physicochemical methods. Examples of the chemical method include an interfacial polycondensation method, an interfacial reaction method (in situ polymerization method), a submerged cured film method (orifice method), and the like. Examples of the physicochemical method include a submerged drying method (in-water drying method and oil-in-water method), a coacervation method, and a melt dispersion cooling method.

  The colored resin particle dispersion according to the present embodiment can be adjusted using, for example, the above-described physicochemical method. In particular, a liquid-in-water drying method can be preferably used, and an oil-in-oil type emulsion-in-oil drying method can be used. Can be used particularly preferably.

  By using the in-oil drying method of an oil-in-oil emulsion, it is possible to adjust colored resin particles having a small average particle size and a narrow particle size distribution using the materials described above, and the viscosity is It is possible to adjust a low colored resin particle dispersion. This makes it possible to obtain an ink that is particularly suitable for ink jet ejection, and to obtain an ink jet ink that is excellent in scratch resistance.

  The colored resin particle dispersion using the oil-in-oil emulsion drying method in oil contains at least a basic dispersant and a non-aqueous solvent (hereinafter, a non-aqueous solvent in a continuous phase may be referred to as a solvent A). Is a continuous phase, a phase containing at least a coloring material, a solid resin, an amphoteric compound and a non-aqueous solvent (hereinafter, the non-aqueous solvent of the dispersed phase may be referred to as solvent B) is defined as the dispersed phase, and the continuous phase and the dispersed phase And an oil-in-oil (O / O) emulsion containing the solvent B, and the solvent B is removed from the dispersed phase.

In order to stably produce an oil-in-oil emulsion, the solvent B preferably has a low solubility in the solvent A. In order to remove the solvent B, the solvent B preferably has a boiling point lower than that of the solvent A.
In order to stably produce an oil-in-oil emulsion, the basic dispersant preferably has higher solubility in the solvent A than the solvent B. In order to stabilize the shape of the colored resin particles, the resin preferably has higher solubility in the solvent B than in the solvent A.

"Continuous phase"
The continuous phase contains solvent A and a basic dispersant.

  The solvent A can be appropriately selected from various non-aqueous solvents so as to satisfy the relationship with the acidic dispersant, the solvent B, and the solid resin described later.

  As the non-aqueous solvent, any of a non-polar organic solvent and a polar organic solvent can be used. These may be used alone or in combination of two or more as long as they form a single phase.

  Preferable examples of the nonpolar organic solvent include petroleum hydrocarbon solvents such as aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, and aromatic hydrocarbon solvents. Examples of the aliphatic hydrocarbon solvent and alicyclic hydrocarbon solvent include paraffinic, isoparaffinic, and naphthenic solvents. For example, what is sold with the following brand names is mentioned. Teclean N-16, Teclean N-20, Teclean N-22, Naphthezol L, Naphthezol M, Naphthezol H, No. 0 Solvent L, No. 0 Solvent M, No. 0 Solvent H, Isosol 300, Isosol 400, AF Solvent No. 4, AF Solvent No. 5, AF Solvent No. 6, AF Solvent No. 7, Cactus Normal Paraffin N12, N13, N14, YHNP, SHNP (all manufactured by JX Nippon Oil & Energy Corporation); Isopar G, Isopar H, Isopar L, Isopar M, Exol D40, Exol D80, Exol D100, Exol D130, and Exol D140 (all manufactured by TonenGeneral Sekiyu KK). Examples of the aromatic hydrocarbon solvent include grade alkene L, grade alkene 200P (all manufactured by JX Nippon Oil & Energy Corporation), Solvesso 200 (manufactured by TonenGeneral Sekiyu KK), and the like. The 50% distillation point of the nonpolar organic solvent is preferably 100 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 200 ° C. or higher. The 50% distillation point means a temperature at which 50% by mass of a solvent is volatilized, which is measured according to JIS K0066 “Testing method for distillation of chemical products”.

As the polar organic solvent, preferred examples of the water-insoluble polar organic solvent include ester solvents, higher alcohol solvents, higher fatty acid solvents and the like. For example, methyl laurate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, isostearyl palmitate, methyl oleate, ethyl oleate, isopropyl oleate, butyl oleate, methyl linoleate, isobutyl linoleate, ethyl linoleate , Isopropyl isostearate, soybean oil methyl, soybean oil isobutyl, tall oil methyl, tall oil isobutyl, diisopropyl adipate, diisopropyl sebacate, diethyl sebacate, propylene glycol monocaprate, trimethylolpropane tri-2-ethylhexanoate, tri Ester solvent having 14 or more carbon atoms in one molecule such as glyceryl 2-ethylhexanoate; isomyristyl alcohol, isopalmityl alcohol, isostear Higher alcohol solvents with 8 or more carbon atoms in one molecule, such as alcohol, oleyl alcohol, etc .; Examples include higher fatty acid solvents having a number of 9 or more.
These can be used alone or in combination of two or more.

  Among these, the solvent A is preferably a nonpolar organic solvent, and more preferably a naphthenic, paraffinic, or isoparaffinic hydrocarbon solvent.

The solvent A preferably has a Hansen solubility parameter (HSP value) of 14 to 18 MPa / cm ³ . The solvent A preferably has a dispersion term δd of 12 to 20, a polar term δp of 0 to 4, and a hydrogen bond term δh of 0 to 4.

  When the solubility parameter of the solvent A is in the above range and the solubility parameter of the amphoteric compound of the colored resin particles and the solid resin is in the above range, the dispersion stability of the colored resin particles in the solvent A can be improved. . Further, when printing using the colored resin particle dispersion, the separation of the colored resin particles and the non-aqueous solvent on the paper can be further promoted, and the fixing property of the colored resin particles to the paper can be further improved, and the resistance can be improved. Abrasion can be further improved. Such a fixing effect can be exhibited more when printed on non-penetrating paper such as coated paper.

As a combination of the solid resin and the solvent A, the following ΔHSP value range is preferably 14-25.
ΔHSP ² = (δd _{solid resin-} δd _{solvent A} ) ² + (δp _{solid resin-} δp _{solvent A} ) ² + (δh _{solid resin-} δh _{solvent A} ) ²

Similarly, as a combination of the amphoteric compound and the solvent A, the range of the following ΔHSP value is preferably 14 to 25.
ΔHSP ² = (δd _{amphoteric compound-} δd _{solvent A} ) ² + (δp _{amphoteric compound-} δp _{solvent A} ) ² + (δh _{amphoteric compound-} δh _{solvent A} ) ²

  By setting ΔHSP in the above range, the dispersion stability of the colored resin particles in the solvent A can be further improved, and the separation of the colored resin particles and the non-aqueous solvent on the paper is further promoted, and the fixing property to the paper is improved. Can be further improved.

  The 50% distillation point of the solvent A is preferably 400 ° C. or lower, more preferably 300 ° C. or lower. On the other hand, the lower limit of the 50% distillation point of the solvent A is preferably 100 ° C. or higher, and 150 ° C. or higher in order to prevent volatilization of the solvent A and maintain the stability of the colored resin particle dispersion. It is more preferable.

The basic dispersant is preferably such that when the basic dispersant is dissolved in a non-aqueous solvent, the oxidation-reduction potential (ORP value) decreases as the concentration of the basic dispersant increases.
For example, when the basic dispersant is dissolved in a solvent capable of dissolving the basic dispersant, the basic dispersant is 5. compared with the ORP value when 0.5% by mass of the basic dispersant is dissolved. It is preferable that the ORP value when 0% by mass is dissolved exhibits a low value.
Further, the ORP value when the basic dispersant is dissolved in 5.0% by mass in dodecane is preferably 0 mV or less.

  On the other hand, when the basic dispersant contains an acidic group together with the basic group, it is preferable as the basic dispersant even if the acidic group is included, as long as the ORP value tends to be low. Can be used. In addition, it is preferable that a basic dispersing agent does not contain an acidic group.

  Examples of the basic group of the basic dispersant include an amino group, an amide group, and a pyridyl group, and among these, an amino group is preferable. Moreover, as a basic group of a basic dispersing agent, the nitrogen-containing functional group which has a urethane bond etc. can be mentioned. Further, a nitrogen-containing structural unit such as a urethane bond may be introduced into the basic dispersant.

  Examples of the basic dispersant include modified polyurethanes, basic group-containing poly (meth) acrylates, basic group-containing polyesters, polyesteramines, quaternary ammonium salts, alkylamine salts such as stearylamine acetate, fatty acid amine salts, and the like. Can be mentioned. You may use these individually or in combination of multiple types.

  Examples of commercially available basic dispersants include “Solsperse 13940 (polyesteramine type), 17000, 18000 (fatty acid amine type), 11200, 22000, 24000, 28000” manufactured by Nippon Lubrizol Co., Ltd. Product name), “DISPERBYK116, 2096, 2163” (all trade names) manufactured by Big Chemie Japan Co., Ltd., “acetamine 24, 86 (alkylamine salt type)” (all trade names) manufactured by Kao Co., Ltd., Enomoto Kasei “Disparon KS-860, KS-873N4 (amine salt of high molecular polyester)” (both are trade names) and the like can be mentioned.

  The basic dispersant preferably has a base number. The base value of the basic dispersant is preferably 1 KOH mg / g or more. As a result, a fine and stable colored resin particle dispersion can be produced.

The basic dispersant preferably includes a (meth) acrylic block polymer having a basic group. Here, “(meth) acrylic block polymer” means a methacrylic block polymer and an acrylic block polymer, and a copolymer containing both methacrylic units and acrylic units in addition to those containing methacrylic units and acrylic units alone. Is also included.
By using a (meth) acrylic block polymer having a basic group as a basic dispersant, the viscosity of the colored resin particle dispersion can be kept low, and the average particle size of the colored resin particles can be reduced. Can do. This makes it possible to obtain an ink that is particularly suitable for inkjet discharge.

As a preferred example of the (meth) acrylic block polymer having a basic group, a block copolymer having a first block containing a unit having an alkyl group having 12 or more carbon atoms and a second block containing a unit having an amino group It is a coalescence.
Thus, the dispersibility of the colored resin particles can be enhanced because the alkyl group portion exhibits solvent affinity and the amino group portion exhibits color resin particle affinity. Moreover, the emulsion stability at the time of emulsion preparation can also be improved. Since it is a block polymer, the alkyl group part is localized and the alkyl group part is easily oriented to the solvent side, so that the solvent affinity can be further increased.

The alkyl group having 12 or more carbon atoms may be a linear or branched alkyl group, and examples thereof include a dodecyl group, a cetyl group, a stearyl group, a behenyl group, an isododecyl group, and an isostearyl group. it can.
These alkyl groups having 12 or more carbon atoms may be contained alone or in combination of two or more in the first block.

As an amino group, for example, a group represented by the general formula —NR ¹ R ² ,
As R ¹ and R ² , groups independently of hydrogen, a hydrocarbon group having 18 or less carbon atoms, an alkanol group having 8 or less carbon atoms, or the like can be used.
Examples of the hydrocarbon group having 18 or less carbon atoms include chain hydrocarbon groups such as methyl group, ethyl group, propyl group, and butyl group, and cyclic hydrocarbon groups such as cyclohexyl group and phenyl group. Examples of the alkanol group having 8 or less carbon atoms include an ethanol group and an isopropanol group.
Preferably, the amino group is a dialkanolamino group represented by the general formula —N (HOR) ₂ (R is a divalent hydrocarbon group).

  The molar ratio of the first block to the second block is preferably 20:80 to 90:10, and more preferably 30:70 to 70:30.

  The first and second blocks may include other groups other than the alkyl group having 12 or more carbon atoms and the amino group of each unit. Examples of other groups include alkyl groups having less than 12 carbon atoms, benzyl groups, and the like.

  As a preferred example of the (meth) acrylic block polymer having a basic group, a monomer containing an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms (hereinafter also referred to as “monomer (A)”). Block A of the mixture a and a block B of the monomer mixture b containing a reactive (meth) acrylate (B) having a functional group capable of reacting with an amino group (hereinafter also referred to as “monomer (B)”) A copolymer (hereinafter, this block copolymer is also simply referred to as “(meth) acrylic block polymer”), and an amino group is introduced by the reaction of a functional group capable of reacting with an amino group and an amino alcohol. It is a thing. Hereinafter, it may be simply referred to as an amine-modified (meth) acrylic block polymer.

  In this amine-modified (meth) acrylic block polymer, the introduced amino alcohol portion serves as an adsorbing group for the colored resin particles, and the alkyl group having 12 or more carbon atoms exhibits solvent affinity, thereby further improving the dispersibility of the colored resin particles. Can be increased.

  Examples of the alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms include dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, and isododecyl (meth). Examples thereof include acrylate and isostearyl (meth) acrylate. These may contain multiple types. Preferably, the alkyl group has 12 to 25 carbon atoms.

  Preferred examples of the functional group capable of reacting with the amino group in the reactive (meth) acrylate (B) include a glycidyl group, a vinyl group, and a (meth) acryloyl group. Examples of the monomer (B) having a glycidyl group include glycidyl (meth) acrylate, and examples of the monomer (B) having a vinyl group include vinyl (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth). ) Acrylate and the like. Examples of the monomer (B) having a (meth) acryloyl group include dipropylene glycol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate. These may contain multiple types.

  Each of the monomer mixtures a and b can contain a monomer (C) that can be copolymerized with these other than the monomers (A) and (B), as long as the effects of the present invention are not impaired.

  Examples of the monomer (C) include styrene monomers such as styrene and α-methylstyrene; vinyl ether polymers such as vinyl acetate, vinyl benzoate, and butyl vinyl ether; maleic acid esters, fumaric acid esters, acrylonitrile, and methacrylonitrile. , Α-olefin and the like. Further, alkyl (meth) acrylates having an alkyl chain length of less than 12 carbons such as 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, tert-octyl (meth) acrylate, and the like can also be used. Further, β-diketone groups such as acetoacetoxyalkyl (meth) acrylate such as 2-acetoacetoxyethyl (meth) acrylate, hexadione (meth) acrylate, acetoacetoxyalkyl (meth) acrylamide such as acetoacetoxyethyl (meth) acrylamide, or the like A (meth) acrylate having a β-keto acid ester group can also be used. These can be used alone or in combination of two or more.

Examples of amino alcohols include monomethylethanolamine, diethanolamine, and diisopropanolamine. Among them, since it is possible to promote adsorption to the interface of the oil-in-oil emulsion by providing two hydroxy groups, the adsorption to the interface of the oil-in-oil emulsion can be promoted. Therefore, the general formula (HOR) ₂ A dialkanolamine (secondary alkanolamine) represented by NH (R is a divalent hydrocarbon group) is preferable. These amino alcohols can also be used in combination of multiple types.

  In order to sufficiently disperse the colored resin particles by introducing the amino group, this amino alcohol is reacted at 0.05 to 1 molar equivalent with respect to the functional group capable of reacting with the amino group of the monomer (B). It is preferable that the reaction is performed at 0.5 to 1 molar equivalent. When the amino alcohol is less than 1 molar equivalent, an unreacted functional group remains in the monomer (B), but the remaining functional group is considered to act as an adsorbing group for the colored resin particles.

  As an example of the synthesis method of the amine-modified (meth) acrylic block polymer, first, in the first stage, one of the monomer mixture a containing the monomer (A) and the monomer mixture b containing the monomer (B) is polymerized and (Meth) acrylic block polymer obtained by polymerizing the other monomer mixture in the presence of the first block in the second stage and polymerizing the other block connected to the end of one block in the second stage. Then, in the third step, this (meth) acrylic block polymer can be reacted with diethanolamine to obtain an amine-modified (meth) acrylic block polymer.

  The molecular weight (mass average molecular weight) of the amine-modified (meth) acrylic block polymer is not particularly limited. However, when used as an inkjet ink, the molecular weight is preferably about 10,000 to 100,000 from the viewpoint of ink ejection. More preferably about 80,000. Furthermore, in the dispersant of this embodiment, the molecular weight is about 20000 to 50000, and excellent dispersion stability can be obtained.

  Since the molecular weight of the amine-modified (meth) acrylic block polymer is almost equal to the molecular weight of the (meth) acrylic block polymer before the reaction with amino alcohol, the molecular weight is adjusted in the polymerization step of the (meth) acrylic block polymer. An amine-modified (meth) acrylic block polymer having a molecular weight in a desired range can be obtained.

  Among the amine-modified (meth) acrylic block polymers, the mass average molecular weight of the block A portion polymerized from the monomer mixture a containing the monomer (A) is preferably about 5000 to 40000, and preferably about 8000 to 30000. Is more preferable. As a result, the solvent affinity of the block A portion can be set in a more suitable range.

  Other examples of the (meth) acrylic block polymer having a basic group include a block A of a monomer mixture a containing an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms, and a reaction having an amino group It is a block copolymer with the block B of the monomer mixture b containing a property (meth) acrylate (B).

  In this example, as the (meth) acrylate (B) having an amino group, a (meth) acrylate having a tertiary amino group can be preferably used. Specifically, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl methacrylamide, dipropylaminoethyl (meth) acrylamide and the like can be used alone or in combination of two or more. .

  In the first stage, the (meth) acrylic block polymer having a basic group is obtained by polymerizing one of the monomer mixture a containing the monomer (A) and the monomer mixture b containing the monomer (B) having an amino group. In the second stage, the other monomer mixture is polymerized in the presence of the first block, and the other block is connected to the end of one block for polymerization.

The basic dispersant in the continuous phase is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass with respect to the entire continuous phase, from the viewpoint of emulsion stability and dispersibility of the colored resin particles. %.
The content of the basic dispersant after removal of the solvent B is preferably from 0.1 to 20% by mass, more preferably from the viewpoint of dispersibility of the colored resin particles, based on the entire colored resin particle dispersion. 1 to 15% by mass.

  To the continuous phase, other optional components such as an antioxidant, a surface tension adjusting agent, and an antifoaming agent may be added as long as the effects of the present invention are not impaired.

"Dispersed phase"
As a dispersed phase, solvent B, a coloring material, a solid resin, and an amphoteric compound are included.

  It is preferable that the solvent B has a solubility in the above-described solvent A of 3 g / 100 g or less at 23 ° C. and a boiling point lower than that of the solvent A.

  The solvent B is preferably a polar organic solvent, and more preferably a lower alcohol solvent. Examples of the lower alcohol solvent include isopropyl alcohol, ethylene glycol, ethanol, methanol, propanol, butanol and the like. More preferably, it is a lower alcohol solvent having 4 or less carbon atoms.

Other specific examples of the solvent B include acetone, methyl ethyl ketone, ethyl acetate, and the like, and further, those satisfying the relationship with the solvent A, the basic dispersant, and the resin can be appropriately selected and used. .
These can be used alone or in combination of two or more.

  The solubility of solvent B in solvent A is preferably 3 g / 100 g at 23 ° C., more preferably 1 g / 100 g or less at 23 ° C., further preferably 0.5 g / 100 g or less, more preferably It does not dissolve substantially.

  The difference in boiling point between the solvent B and the solvent A is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and still more preferably 50 ° C. or higher. In this case, in the case of a mixed solvent such as a petroleum hydrocarbon solvent, the boiling point is 50% distillation point. Moreover, it is preferable that the boiling point of the solvent B is 100 degrees C or less, More preferably, it is 90 degrees C or less. On the other hand, the lower limit of the boiling point of the solvent B is not particularly limited as long as the solvent B is liquid in the range of −20 to 90 ° C.

The solvent B preferably has a Hansen solubility parameter (HSP value) of 18 to 30 MPa / cm ³ , more preferably 20 to 30 MPa / cm ³ . The solvent B preferably has a dispersion term δd of 14 to 17, a polar term δp of 5 to 15, and a hydrogen bond term δh of 5 to 25, more preferably a dispersion term δd of 14 to 17 and a polar term. δp is 5 to 15 and hydrogen bond term δh is 15 to 25.

  When the solubility parameter of the solvent B is in the above range, the solubility in the solvent A is low and the colored resin particles and the solid resin can be dissolved. If the solubility parameter of the colored resin particles and the solid resin is in the above range, it can be dissolved in the solvent B, insoluble in the solvent A, and obtain dispersion stability.

  Moreover, it is preferable that the solvent A is a hydrocarbon solvent and the solvent B is an alcohol solvent having 4 or less carbon atoms. Preferable examples of the hydrocarbon solvent include naphthene, paraffin, isoparaffin, and the like, and preferable examples of the alcohol solvent having 4 or less carbon atoms include methanol, ethanol, propanol, butanol, and more preferably methanol. .

  The color material is as described above.

  The colorant preferably has higher solubility in the solvent B than in the solvent A, so that the resin is dissolved in the solvent B together with the dye in the dispersed phase, so that the colored resin particle dispersion can be stably provided.

  Here, the colorant preferably has a solubility in the solvent A of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less, and still more preferably 0.1 g / 100 g or less. In addition, the colorant preferably has a solubility in the solvent B of 0.5 g / 100 g or more at 23 ° C., more preferably 1 g / 100 g or more. More preferably, the dye is selected so that the coloring material is substantially completely dissolved in the solvent B and the coloring material is not substantially dissolved in the solvent A in the blending ratio of the oil-in-oil emulsion.

  The colorant is preferably an oil-soluble dye that is soluble in the resin in the dispersed phase. In particular, phthalocyanine dyes are preferable.

The coloring material in the dispersed phase is preferably from 0.1 to 50% by mass, more preferably from 1 to 40% by mass, and even more preferably from 2 to 40% by mass, based on the total amount of the dye and the pigment. 20% by mass. Thereby, the solubility or dispersibility in the solvent B can be stabilized.
After the removal of the solvent B, the content of the coloring material is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass with respect to the entire colored resin particle dispersion as the total amount of the dye and the pigment. %, More preferably 2 to 20% by mass. Thereby, the coloring of the colored resin particles can be made appropriate and the shape can be stabilized.

The solid resin is preferably a solid resin at room temperature (23 ° C.). Details are as described above.
This solid resin preferably has a higher solubility in the solvent B than the solvent A when the colored resin particles are produced by an oil-in-oil emulsion.

  The solubility of the resin in the solvent B is preferably 10 g / 100 g or more at 23 ° C., more preferably 20 g / 100 g or more. Moreover, it is preferable that the solubility with respect to the solvent A of resin is 3 g / 100g or less at 23 degreeC, More preferably, it is 0.5 g / 100g or less. More preferably, the resin is one that substantially dissolves in the solvent B and does not substantially dissolve in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the solid resin with respect to the total amount of the dispersed phase is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 20% by mass. Thereby, the solubility of the solid resin in the solvent B can be made appropriate, and the components of the colored resin particles can be made more uniform.
The content of the solid resin relative to the total amount of the colored resin particle dispersion after removal of the solvent B is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass. Thereby, the coloring of the colored resin particles can be made appropriate and the shape can be stabilized.

The solid resin in the dispersed phase is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 to 20% by mass with respect to the total amount of the dispersed phase. Thereby, the solubility of the resin in the solvent B can be made appropriate, and the components of the colored resin particles can be made more uniform.
The content of the solid resin after removal of the solvent B is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, and still more preferably 2 with respect to the total amount of the colored resin particle dispersion. ˜20 mass%. Thereby, the coloring of the colored resin particles can be made appropriate and the shape can be stabilized.

  The mass ratio of the solid resin to the coloring material is preferably (solid resin mass) / (coloring material mass) ≧ 0.5. Within this range, when the continuous phase and the dispersed phase are mixed and stirred, an oil-in-oil emulsion excellent in emulsion stability can be provided.

The details of the liquid organic compound having an acidic group and a basic group are as described above.
By adding the amphoteric compound, the abrasion resistance of the printed material can be further improved. This is because the amphoteric compound makes it possible to blend the color material and the solid resin more uniformly and stably.
In addition, when a resin with a low acid value and high water resistance is used as the solid resin, the wear resistance may be reduced. By adding an amphoteric compound together with this solid resin, the water resistance and the wear resistance are improved. Can be made.
Moreover, the amphoteric compound can further improve the stability of the oil-in-oil emulsion in the production process of the colored resin particle dispersion.

  The amphoteric compound is not particularly limited, but preferably has higher solubility in the solvent B than the solvent A. The solubility of the amphoteric compound in the solvent B is preferably 1 g / 100 g or more at 23 ° C., more preferably 2 g / 100 g or more. The solubility of the amphoteric compound in the solvent A is preferably 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. More preferably, the amphoteric compound is one that substantially dissolves in the solvent B and does not substantially dissolve in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the amphoteric compound with respect to the total amount of the dispersed phase is preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass. Thereby, the emulsion can be further stabilized.
The content of the amphoteric compound relative to the total amount of the colored resin particle dispersion after removal of the solvent B is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass. Thereby, the wear resistance can be further improved.

The amphoteric compound in the dispersed phase is preferably from 0.1 to 25 mass%, more preferably from 1 to 20 mass%, based on the entire dispersed phase. Thereby, the emulsion can be further stabilized.
The content of the amphoteric compound after removal of the solvent B is preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass with respect to the entire colored resin particle dispersion. Thereby, the wear resistance can be further improved.

  The mass ratio of the amphoteric compound and the color material is preferably (mass of amphoteric compound) / (mass of color material) ≧ 0.5. Within this range, when the continuous phase and the dispersed phase are mixed and stirred, an oil-in-oil emulsion excellent in emulsion stability can be provided.

  Other optional components such as an antifoaming agent, an antioxidant, a surface tension adjusting agent, and a crosslinking agent may be added to the dispersed phase as long as the effects of the present invention are not impaired. The above-described plasticizer may be added to the dispersed phase.

"Method of adjusting dispersion"
The method for preparing the colored resin particle dispersion is not particularly limited, and an oil-in-oil emulsion is prepared by dispersing the above-described dispersed phase in the above-described continuous phase. From this oil-in-oil emulsion, the pressure is reduced and / or heated. It can be adjusted by removing the non-aqueous solvent B in the dispersed phase.

  For example, the continuous phase and the dispersed phase can be adjusted by mixing the above-described components. Thereafter, the dispersed phase can be dispersed in the continuous phase by mixing and stirring while dropping the dispersed phase in the continuous phase. At this time, mixing and stirring can be performed using an ultrasonic homogenizer. The non-aqueous solvent B is removed from the obtained oil-in-oil emulsion by reducing pressure and / or heating. At this time, the degree of pressure reduction and / or heating is adjusted so that the non-aqueous solvent B is removed, but the non-aqueous solvent A remains.

  When a pigment is used for the colorant, a general wet disperser such as a ball mill, a bead mill, an ultrasonic wave, a homomixer, or a high-pressure homogenizer can be used as a method for dispersing the pigment in the dispersed phase.

  Moreover, the mass ratio of the continuous phase and the dispersed phase of the oil-in-oil emulsion can be adjusted in the range of 40:60 to 95: 5. The addition amount of the non-aqueous solvent B is preferably 5 to 40% by mass, more preferably 5 to 30% by mass with respect to the whole oil-in-oil emulsion. The removal amount of the non-aqueous solvent B is preferably the total amount of the non-aqueous solvent B blended, but may be 90% by mass or more with respect to the total amount of the non-aqueous solvent B blended.

  Other examples of the method for producing the colored resin particle dispersion include, for example, separately adjusting the components of the dispersed phase as a plurality of mixed liquids, and dropping each mixed liquid simultaneously or sequentially onto the continuous phase, Medium oil emulsion can be prepared.

  Specifically, for example, a phase containing at least a basic dispersant and a non-aqueous solvent (solvent A) is used as a continuous phase, does not include a coloring material and a solid resin, and includes at least an amphoteric compound and a non-aqueous solvent (solvent B). The phase is a dispersed phase, and the continuous phase and the dispersed phase are mixed to produce an oil-in-oil (O / O) type pre-emulsion, and this pre-emulsion contains a coloring material, a solid resin and a non-aqueous solvent (solvent B). It is also possible to use a method obtained by further adding a mixed liquid to prepare an oil-in-oil (O / O) emulsion, and then removing the solvent B added as a dispersed phase and mixed liquid by reducing pressure and / or heating. it can. Hereinafter, this method may be referred to as a two-stage emulsification method.

In order to stably produce an oil-in-oil emulsion, the solvent B preferably has a low solubility in the solvent A. In order to remove the solvent B, the solvent B preferably has a boiling point lower than that of the solvent A.
In order to stably produce an oil-in-oil emulsion, the basic dispersant preferably has higher solubility in the solvent A than the solvent B. In order to stabilize the shape of the colored resin particles, the solid resin preferably has higher solubility in the solvent B than the solvent A.

In this two-stage emulsification method, it is possible to provide finer colored resin particles by preventing the aggregation of the coloring material in the process of producing the colored resin particles. In the production process of the colored resin particles, the coloring material may act and aggregate with other components, particularly the amphoteric compound, but according to this two-stage emulsification method, the coloring material can be added alone afterwards. , Such aggregation can be prevented.
The colored resin particles having a fine particle size are particularly suitable for inkjet inks.

  In the two-stage emulsification method, each component used in the oil-in-oil emulsion is the same as described above unless otherwise specified. As a color material, the problem of aggregation can be improved in both pigments and dyes.

In the continuous phase, the blending amounts of the basic dispersant and the solvent A are the same as those in the one-stage emulsification method described above.
In the dispersed phase, the amphoteric compound is preferably 1 to 70% by mass, more preferably 10 to 50% by mass, based on the entire dispersed phase.
In the mixed solution, the coloring material is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the entire mixed solution. When the color material is a pigment, a pigment dispersant can be further added to the mixed solution.
In the mixed solution, the solid resin is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass with respect to the entire mixed solution.

  The colored resin particle dispersion obtained by the two-stage emulsification method preferably contains each component in a predetermined ratio as in the above-described one-stage emulsification method.

In the colored resin particle dispersion, the average particle diameter of the colored resin particles is preferably as described above.
The average particle diameter of the colored resin particles can be controlled by adjusting the amount of the basic dispersant blended in the continuous phase or the amount of the nonvolatile component blended in the dispersed phase. By blending the amphoteric compound, the average particle diameter of the colored resin particles can be controlled to be smaller.

(ink)
The ink according to this embodiment is an ink containing the above-described colored resin particle dispersion. This ink can be used as a general printing ink such as inkjet printing, offset printing, stencil printing, and gravure printing. In particular, since the dispersion stability is good, it is preferably used as an inkjet ink.

  When used as an ink-jet ink, the colored resin particle dispersion can be used as it is, and if necessary, various additives usually used in the field within a range not impairing the object of the present invention. Can be included. For example, a nozzle clogging preventive agent, an antioxidant, a conductivity adjusting agent, a viscosity adjusting agent, a surface tension adjusting agent, an oxygen absorbent and the like can be added as appropriate. These types are not particularly limited, and those used in the field can be used. Further, the colored resin particle dispersion may be diluted with the non-aqueous solvent described above.

  The viscosity of the inkjet ink varies depending on the nozzle diameter of the ejection head of the inkjet recording system, the ejection environment, and the like, but in general, the viscosity is preferably 5 to 30 mPa · s at 23 ° C., preferably 5 to 15 mPa · s. It is more preferable that it is about 10 mPa · s. Here, the viscosity represents a value at 10 Pa when the shear stress is increased from 0 Pa at a rate of 0.1 Pa / s at 23 ° C.

  The printing method using the inkjet ink is not particularly limited, and any method such as a piezo method, an electrostatic method, or a thermal method may be used. When an ink jet recording apparatus is used, it is preferable that the ink according to the present embodiment is ejected from the ink jet head based on a digital signal, and the ejected ink droplets are attached to the recording medium.

  In the present embodiment, the recording medium is not particularly limited, and printing paper such as plain paper, coated paper, special paper, cloth, inorganic sheet, film, OHP sheet, etc., and these are used as a base material and an adhesive layer on the back surface An adhesive sheet or the like provided with can be used. Among these, printing paper such as plain paper and coated paper can be preferably used from the viewpoint of ink permeability.

  Here, the plain paper is paper in which an ink receiving layer, a film layer, and the like are not formed on normal paper. Examples of plain paper include high quality paper, medium quality paper, PPC paper, reprinted paper, recycled paper, and the like. Plain paper is a paper in which ink easily penetrates because paper fibers having a thickness of several μm to several tens of μm form voids of several tens to several hundreds of μm.

  Further, as the coated paper, inkjet coated paper or so-called coated printing paper can be preferably used. Here, the coated printing paper is a printing paper conventionally used in letterpress printing, offset printing, gravure printing, etc., and has an inorganic pigment such as clay or calcium carbonate on the surface of high-quality paper or medium-quality paper. A printing paper provided with a coating layer by a paint containing a binder such as starch. Coated printing paper can be applied to fine coated paper, high-quality lightweight coated paper, medium-weight lightweight coated paper, high-quality coated paper, medium-quality coated paper, art paper, cast coated paper, etc., depending on the coating amount and coating method. being classified. Coated printing paper has fewer voids on the paper surface than plain paper and inkjet coated paper, so that ink penetration is slow and ink components tend to stay on the paper surface. Therefore, the ink according to the present embodiment is suitable for improving the fixing property to the coated printing paper.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Unless otherwise specified, “%” indicates “mass%”.

<Ink adjustment>
Tables 2 and 3 show the formulations of the oil-in-oil emulsions of Examples and Comparative Examples before removing the solvent B. In each table, when the volatile matter is contained in the dispersant, the nonvolatile content is shown in parentheses together with the total amount of the dispersant (Tables 4 and 5 described later are also the same).

  Solvent A and a basic dispersant were mixed in the blending amounts shown in each table to prepare a continuous phase. Next, the dispersion phase was adjusted by mixing a dye, a solid resin and an amphoteric compound with the solvent B in the blending amounts shown in each table.

  While stirring the continuous phase with a magnetic stirrer, an ultrasonic homogenizer “Ultrasonic processor VC-750” (manufactured by Sonics) was irradiated for 10 minutes while adding a pre-mixed dispersed phase dropwise to the continuous phase. An oil-in-oil (O / O) emulsion was obtained.

  (4) Solvent B in the dispersed phase was removed while reducing the pressure of the obtained emulsion with an evaporator to obtain a colored resin particle dispersion. The removal rate of the solvent B was almost 100% by mass. This colored particle dispersion was used as an ink as it was.

The inks of Examples and Comparative Examples were prepared in the same manner as described above except as described below.
In Comparative Examples 1 and 2, the amphoteric compound was not added to the dispersed phase.
In Comparative Examples 2 to 4, the acidic dispersant was added without adding the basic dispersant to the continuous phase.

In the ink of each example, the colored resin particles were stably dispersed.
In Comparative Example 1, ink could be prepared with sufficient emulsification stability.
In Comparative Examples 2 to 4, the emulsion stability was low, and the ink could not be adjusted.

  Tables 4 and 5 show the ink formulations of Examples and Comparative Examples after removal of solvent B.

The components shown in each table are as follows.
(Continuous phase)
Hydrocarbon solvent: Isoparaffin hydrocarbon, “Isopar M” manufactured by TonenGeneral Sekiyu KK
Basic dispersant “S17000”: “Solsperse 17000” manufactured by Nippon Lubrizol Co., Ltd., non-volatile content 100%, base number 2 KOH mg / g.

(Dispersed phase)
Methanol: C1-C1 alcohol solvent, manufactured by Wako Pure Chemical Industries, Ltd.
Phthalocyanine dye “Valifast Blue 1605”: a dye containing “Valifast Blue 1605” manufactured by Orient Chemical Industry Co., Ltd., Solvent Blue 38 and the like.
Metal complex dye “Valifast Red 3311”: “Valifast Red 3311” manufactured by Orient Chemical Industry Co., Ltd., dye containing Solvent Red 8 and the like.
Polyvinyl alcohol: “JMR-8L” manufactured by Nihon Vineyard-Poval, saponification degree 2.7 mol%, and mass average molecular weight 15000.
Amphoteric compound “DISPERBYK-180”: alkylammonium salt of block copolymer having acidic group, “DISPERBYK-180” manufactured by BYK Japan KK, acid value 94 KOH mg / g, base value 94 KOH mg / g, nonvolatile content 81.0 %.
Amphoteric compound “DISPERBYK-145”: phosphate ester salt of copolymer having basic group, “DISPERBYK-145” manufactured by Big Chemie Japan KK, acid value 76 KOH mg / g, base value 71 KOH mg / g, nonvolatile content 95. 0%.
Amphoteric compound "DISPERBYK-9076": alkylammonium salt of polymer copolymer, dispersant having acidic group and basic group, "DISPERBYK-9076" manufactured by Big Chemie Japan, acid value 38KOHmg / g, base value 44KOHmg / G, nonvolatile content 96.0%.
Amphoteric compound “DISPERBYK-191”: an amphoteric acetate copolymer having an amine group and a carboxylic acid group, which is a polyacrylic acid resin, “DISPERBYK-191” manufactured by BYK Japan Japan, acid value 30 KOH mg / g, base number 20 KOH mg / G, 98% non-volatile content.

  Methanol as the solvent B has a solubility in a hydrocarbon solvent (Isopar M) as the solvent A of 0.4 g / 100 g at 23 ° C. The boiling point of methanol is 64.7 ° C., and the 50% distillation point of Isopar M is about 234 ° C.

Solsperse 17000, which is a basic dispersant, was dissolved in the solvent A at the blending ratio of the continuous phases shown in Tables 2 and 3, and the solubility in the solvent B was less than 3 g / 100 g at 23 ° C.
Polyvinyl alcohol as a resin, dissolved in the solvent B at the blending ratio of the dispersed phases shown in Table 2 and Table 3, the solubility in the solvent A is less than 3 g / 100 g at 23 ° C., and the solubility in water is 3 g / 100 g at 23 ° C. Was less than.
The dye and the amphoteric compound were each dissolved in the solvent B at the mixing ratio of the dispersed phases shown in Table 2 and Table 3, and the solubility in the solvent A was less than 3 g / 100 g at 23 ° C.

The solubility parameter (HSP value) of each component is as follows. The unit is “MPa / cm ³ ”. The dispersion term δd, the polar term δp, and the hydrogen bond term δh are also shown.
Solvent A “Isopar M”: 16 (δd = 16, δp = 0, δh = 0).
Solvent B “methanol”: 29.6 (δd = 15.1, δp = 12.3, δh = 22.3).
Solid resin: 22-27 (δd = 12-20, δp = 5-12, δh = 10-20).
Various amphoteric compounds: 22-27 (δd = 12-20, δp = 5-12, δh = 10-20).

The oxidation-reduction potential (ORP value) of each component is as follows. The unit is “mV”.
Solsperse 17000: ORP value when 5.0% by mass is dissolved compared to ORP value when 0.5% by mass is dissolved in dodecane, ORP value when 5.0% by mass is dissolved in dodecane Was 325.
Various amphoteric compounds: The ORP value when dissolved in methanol by 5.0% by mass was 0-200.

<Evaluation>
The following evaluations were performed using the inks described above. The results are shown in each table.

(Emulsifying)
When the colored resin particle dispersion was adjusted according to the above process, the emulsifiability was evaluated according to the following criteria.
AA: An oil-in-oil emulsion could be prepared and there was no precipitate after removal of solvent B in the dispersed phase.
A: An oil-in-oil emulsion could be prepared, and there was little precipitate after removing the solvent B in the dispersed phase.
B: An oil-in-oil emulsion could be prepared, but there were many precipitates after removing the solvent B in the dispersed phase.
C: An oil-in-oil emulsion could not be prepared.

(Abrasion resistance)
Each of the inks described above is loaded into a line-type ink jet printer “Orpheus X9050” (made by Riso Kagaku Co., Ltd.), and a solid image is printed on high-quality coated paper “Aurora Coat” (made by Nippon Paper Industries Co., Ltd.). Obtained. Printing was performed at a resolution of 300 × 300 dpi under an ejection condition where the ink amount per dot was 42 pl. Note that “Orpheus X9050” is a system that uses a line-type inkjet head and conveys paper in the sub-scanning direction orthogonal to the main scanning direction (the direction in which the nozzles are arranged) to perform printing.

After standing for 24 hours after printing, the state when the solid image portion of the printed material was strongly rubbed with a finger five times was visually observed, and the scratch resistance was evaluated according to the following criteria.
A: Level at which image peeling is hardly observed.
B: A level at which peeling of the image is confirmed but there is no problem in actual use.
C: Image peeling is remarkable and there is a problem in actual use.

(water resistant)
A printed matter was obtained in the same manner as the above-mentioned scratch resistance. After standing for 24 hours after printing, 0.5 ml of water was dropped on the solid image portion of the printed matter, and the bleeding was visually observed to evaluate the water resistance according to the following criteria.
A: Level at which the printed image portion does not blur.
B: A level at which there is no problem in actual use although the printed image portion is slightly blurred.
C: The level where the printed image portion is blurred and there is a problem in actual use.

(Marker resistance)
A printed matter was obtained in the same manner as the scratch resistance described above, except that characters were printed instead of the solid image. After leaving for 24 hours after printing, draw a line on the characters on the printed part of the coated paper with the line marker pen “PM-L103Y” manufactured by KOKUYO Co., Ltd. evaluated.
A: A level in which the printed image portion is not stained or the periphery of the printed image portion is slightly stained.
B: A level at which there is no problem in actual use although the periphery of the printed image portion is dirty.
C: The area around the printed image is a level where there is a problem in actual use.

(Average particle diameter of colored resin particles)
For each of the inks described above, the volume-based average particle diameter of the colored resin particles dispersed in the ink was measured using a dynamic light scattering particle size distribution measuring device “LB-500” (manufactured by Horiba, Ltd.). did.

As shown in the respective tables, the inks of the respective examples had good evaluations, and the average particle diameter of the colored resin particles was in an appropriate range.
In each Example, by including the liquid organic compound (amphoteric compound) which has an acidic group and a basic group, it was excellent in emulsifiability and could improve abrasion resistance, water resistance, and marker resistance.
In Examples 1 to 3, the amphoteric compound had a larger acid value and base value, and was superior in emulsion stability when combined with a phthalocyanine dye.

In Comparative Example 1, no amphoteric compound was added, and the scratch resistance and marker resistance were lowered.
In Comparative Example 2, the amphoteric compound was not added, and the continuous phase dispersant was acidic, and the emulsifiability was lowered, making it impossible to adjust the ink.
In Comparative Examples 3 and 4, although the amphoteric compound was included, the continuous phase dispersant was acidic, and the emulsification was lowered, making it impossible to prepare the ink.

Claims (6)

  A colored resin particle dispersion comprising colored resin particles, a basic dispersant, and a non-aqueous solvent, wherein the colored resin particles comprise a color material, a solid resin, and a liquid organic compound having an acidic group and a basic group. .   The colored resin particle dispersion according to claim 1, wherein the coloring material is a phthalocyanine dye.   The colored resin according to claim 1 or 2, wherein the liquid organic compound having an acidic group and a basic group includes a phosphate ester salt of a resin having a basic group and / or an alkyl ammonium salt of a resin having an acidic group. Particle dispersion.   The colored organic resin particles according to any one of claims 1 to 3, wherein the liquid organic compound having an acidic group and a basic group has an acid value of 30 KOHmg / g or more and a base value of 30 KOHmg / g or more. Dispersion. Using a non-aqueous solvent A and a non-aqueous solvent B having a boiling point lower than that of the non-aqueous solvent A,
In a continuous phase containing the non-aqueous solvent A and the basic dispersant, a dispersed phase containing the non-aqueous solvent B, the coloring material, the solid resin, and a liquid organic compound having the acidic group and the basic group. Disperse to make an oil-in-oil emulsion,
The non-aqueous solvent B is removed from the oil-in-oil emulsion,
The basic dispersant has higher solubility in the non-aqueous solvent A than the non-aqueous solvent B,
The liquid organic compound having the solid resin and the acidic group and the basic group has higher solubility in the non-aqueous solvent B than the non-aqueous solvent A.
The colored resin particle dispersion according to any one of claims 1 to 4.   An inkjet ink comprising the colored resin particle dispersion according to any one of claims 1 to 5.