JP6263031B2 - Colored resin particle dispersion and inkjet ink - Google Patents

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, a pigment can improve water resistance and marker resistance as compared with a dye. A color material excellent in both scratch resistance, water resistance and marker resistance is desired.

  On the other hand, by including the coloring material in the form of colored resin particles by providing the coloring material, an ink that is excellent in water resistance and marker resistance as well as scratch resistance while using the coloring property of the coloring material is provided. There is a way. Here, as the resin, it is desirable that the ink has a property of imparting scratch 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 the printing ink is prepared using these polymer particle dispersions, the water resistance, marker resistance and scratch resistance of an ink image printed on paper or the like have not been studied in the above literature. When a resin that improves the water resistance, marker resistance, and scratch resistance of the ink is used as the resin of the dispersed phase in the above document, it is difficult to maintain the stability of 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.

  Further, it is preferable that the ink is stored stably for a long period of time while maintaining dispersibility. Moreover, it may be stored in a high temperature environment. Therefore, when selecting the type of resin in order to impart scratch resistance, water resistance and marker resistance to the ink, it is desired to improve the storage stability of the ink and prevent the generation of odors.

  An object of the present invention is to provide a colored resin particle dispersion and an ink having excellent wear resistance and less odor. It is another object of the present invention to provide a colored resin particle dispersion and an inkjet ink that are excellent in water resistance, marker resistance, and storage stability, as well as improved abrasion resistance and odor prevention.

  As one aspect of the present invention, it includes colored resin particles containing a colorant, a solid resin, and a liquid organic compound having an acidic group, a basic dispersant, and a non-aqueous solvent, wherein the solid resin is (1) A colored resin particle dispersion comprising one or more of a polyvinyl acetal resin having an acetyl group of 10 mol% or less, (2) an alkylphenol resin, and (3) a ketone resin.

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

  According to the present invention, it is possible to provide a colored resin particle dispersion and ink that are excellent in wear resistance and have less odor. Furthermore, it is possible to provide a colored resin particle dispersion and an inkjet ink that are excellent in water resistance, marker resistance, and storage stability, as well as improved abrasion resistance and odor prevention.

  A colored resin particle dispersion (hereinafter sometimes simply referred to as “dispersion”) according to an embodiment of the present invention includes a color material, a solid resin, and a liquid organic compound having an acidic group (hereinafter simply referred to as “acidic compound”). The solid resin comprises (1) a polyvinyl acetal resin having an acetyl group of 10 mol% or less, and (2) an alkylphenol resin. And (3) one or more of ketone resins.

  Thereby, it is possible to provide a colored resin particle dispersion and ink having excellent wear resistance and less odor. Furthermore, it is possible to provide a colored resin particle dispersion and ink that are excellent in water resistance, marker resistance, and storage stability, as well as improved abrasion resistance and odor prevention.

According to the present inventors, by using polyvinyl alcohol as the solid resin constituting the colored resin particles, it has been found that the ink has excellent water resistance and marker resistance as well as abrasion resistance, particularly scratch resistance.
However, in ink using colored resin particles containing polyvinyl alcohol, there may be a problem that an odor is generated after a certain period of time. In particular, there may be a problem during storage at a high temperature of 70 ° C. or higher. This is considered that the acetyl group contained in the polyvinyl alcohol reacts with lower alcohol and water in the ink to produce methyl acetate and acetic acid, which causes odor as an acetic acid odor.

  Then, generation | occurrence | production of an odor can be prevented by using the solid resin of said (1)-(3) as solid resin which comprises a colored resin particle. Furthermore, by using these solid resins, it is possible to improve water resistance and marker resistance as well as abrasion resistance while suppressing the generation of odor as an ink. In addition, the storage stability at high temperatures can be improved.

(Colored resin particles)
The colored resin particles according to the present embodiment include a color material, a solid resin, and an acidic compound.
The colored resin particles preferably have a particle shape in which a color material, a solid resin, and an acidic compound are uniformly mixed.

"Solid resin"
The solid resin is at least one selected from (1) a polyvinyl acetal resin having an acetyl group of 10 mol% or less, (2) an alkylphenol resin, and (3) a ketone resin. These solid resins are preferably solid resins 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.

Here, since the polyvinyl alcohol (PVA) resin is a resin having excellent water resistance, the printed resin has water resistance as well as abrasion resistance and marker resistance by including the PVA resin in the colored resin particles. Can do.
On the other hand, when the PVA resin is contained in the colored resin particles, there is a problem that an acetic acid odor is generated. This is because the PVA resin is generally produced by using polyvinyl acetate as a raw material and substituting the acetate group of polyvinyl acetate with a hydroxyl group, so that it contains an acetate group together with a hydroxyl group according to the ratio of substitution. Resin. Therefore, when the PVA resin is contained in the colored resin particles, a part of the acetate group of the PVA resin is separated and generated as methyl acetate or acetic acid, which is considered to cause acetic acid odor.

  Moreover, when the acetate group of PVA resin is reduced, it will become difficult to manufacture colored resin fine particles. This is because the solubility in the solvent decreases when the PVA resin and other components are mixed in the manufacturing process of the colored resin fine particles.

  Therefore, as with the PVA resin, when examining resins capable of providing colored resin particles having excellent water resistance as well as wear resistance and marker resistance, the finding that the solid resins (1) to (3) above are suitable. Obtained.

  (1) 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.

  Polyvinyl alcohol is generally a resin produced by using polyvinyl acetate as a raw material and substituting the acetate group of polyvinyl acetate with a hydroxyl group, and containing an acetate group together with the hydroxyl group according to the substitution ratio.

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, the saponification degree is (n / (N + m) × 100, and the degree of polymerization is represented by n + m.

  The degree of saponification (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 acetyl group of 10 mol% or less, more preferably 5 mol% or less, and still more preferably 3 mol% or less. Thereby, the generation of acetic acid odor can be prevented.
On the other hand, the lower limit of the acetyl group in the polyvinyl acetal resin is not particularly limited, and is usually 0 mol%.

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

  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.

The mass average molecular weight (Mm) of the polyvinyl acetal resin is preferably 10,000 to 200,000, more preferably 20,000 to 100,000. 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.
In order to stably store the colored resin particles in the solvent, the mass average molecular weight of the polyvinyl acetal resin is more preferably 60000 or less, and further preferably 30000 or less.

  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 glass transition temperature (Tg) of the polyvinyl acetal resin is preferably 100 ° C. or less, more preferably 80 ° C. or less, from the viewpoint of the shape stability and component uniformity of the colored resin particles.

  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.

  (2) The alkylphenol resin may be any of a novolak type alkylphenol resin and a resol type alkylphenol resin, or a combination thereof.

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.

  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.

  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 mass average molecular weight of the alkylphenol resin is preferably 10,000 to 200,000, more preferably 20,000 to 100,000. 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 resin can be mixed uniformly with a solvent, and as a result, colored resin particles with uniform components can be provided.

  The softening point (ring and ball method) of the alkylphenol resin is preferably 30 to 200 ° C., more preferably 50 to 150 ° C., from the viewpoint of the shape stability and component uniformity of the colored resin particles.

Commercially available alkylphenol resins include Tamanoru series “100S”, “200N”, “7509”, “PA”, etc. manufactured by Arakawa Chemical Industries, Ltd .; Etc. can be used.
These may be used alone or in combination of two or more.

  (3) As a ketone resin, what is manufactured by making a ketone and an aldehyde react in presence of an alkali catalyst can be used.

  Examples of ketones include acetone, cyclohexanone, acetophenone, methyl ethyl ketone, methyl isobutyl ketone, methyl cyclohexanone, isophorone, and combinations thereof.

  Examples of aldehydes include formaldehyde, acetaldehyde, butyraldehyde, paraformaldehyde, trioxane, tetraoxane, and combinations thereof.

  A polyaryl ketone resin may be used as the ketone resin. Examples of the polyaryl ketone resin include polyether ketone, polyether ether ketone, and combinations thereof.

  The mass average molecular weight of the ketone resin is preferably 1000 to 100,000, more preferably 2000 to 50000. 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 resin can be mixed uniformly with a solvent, and as a result, colored resin particles with uniform components can be provided.

  The softening point (ring and ball method) of the ketone resin is preferably 30 to 200 ° C., more preferably 50 to 150 ° C., from the viewpoint of shape stability and component uniformity of the colored resin particles.

Examples of commercially available ketone resins include ketone resin “K90” manufactured by Arakawa Chemical Co., Ltd .; Vestakeep series “1000G”, “2000G”, “3001G” manufactured by Daicel Evonik Co., Ltd .; Daicel Evonik Co., Ltd. “Vesta Keep 2000G” (polyetheretherketone resin) manufactured by the company can be used.
These may be used alone or in combination of two or more.

The amount of the solid resin described above is preferably 10% by mass or more, more preferably 30% 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%.

  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. Examples of other resins include pigment dispersants and additives as described in the method for producing a colored resin particle dispersion described later.

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.

"Coloring material"
The color material contained in the colored resin particles may be either a pigment or a dye, or a combination thereof. Details will be described later. According to the method for producing colored resin particles described later, it is preferably an oil-soluble dye, and more preferably a metal complex dye.

  The coloring material is preferably blended in an amount of 0.1 to 50% by mass, more preferably 1 to 40% by mass, from the viewpoint of colorability and uniformity of the components with respect to the entire colored resin particles. More preferably, it is 2-20 mass%.

"Acid compounds"
The colored resin particles contain a liquid organic compound (acidic compound) having an acidic group. Here, the liquid organic compound having an acidic group is an organic compound that is liquid at 23 ° C. and has an acidic group.

By adding an acidic compound, the color developability and abrasion resistance of the printed matter can be further improved. This is because it is possible to mix the colorant and the solid resin more uniformly and stably by the acidic compound.
Moreover, an acidic compound can be mix | blended in order to maintain stability of an oil-in-oil emulsion in the manufacturing process of a colored resin particle dispersion.

  The melting point of the acidic compound is preferably 23 ° C. or lower, more preferably 15 ° C. or lower in order to maintain a liquid state at room temperature.

When the acidic compound is dissolved in a non-aqueous solvent, the oxidation-reduction potential (ORP) value is preferably increased as the concentration of the acidic compound increases.
For example, when the acidic compound is dissolved in a solvent capable of dissolving the acidic compound, when the acidic compound is dissolved by 5.0% by mass, compared to the ORP value when the acidic compound is dissolved by 0.5% by mass. It is preferable that the ORP value is a high value.
In addition, the ORP value when the acidic compound is dissolved in methanol by 5.0% by mass is preferably 200 mV or more, more preferably 300 mV or more.

  On the other hand, when the acidic compound contains a basic group together with the acidic group, it can be preferably used as the acidic compound even if the basic group is contained, as long as the ORP value tends to be high. . In addition, it is more preferable that an acidic compound does not contain a basic group.

  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. 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”. The same applies hereinafter.

As the solubility parameter of the acidic compound, the Hansen solubility parameter (HSP value) is preferably 22 to 27 MPa / cm ³ . The acidic 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 acidic compound include a phosphoric acid group, a carboxy group, a sulfonic acid group, a phosphoric ester group, a sulfuric ester group, a nitric 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. It is preferable to have two or more acidic groups in one molecule of the acidic compound.

The acidic compound may be an oligomer, a polymer, or a low molecular weight compound.
As the oligomer or polymer, for example, poly (meth) acrylic resins, polyester resins, polyvinyl resins, polyether resins and the like can be used alone or in combination. Moreover, you may use the copolymer of the monomer or oligomer which comprises these resin.

As an acidic group, it originates from the monomer which comprises an oligomer or a polymer, and the acidic group may couple | bond and introduce | transduce into the principal chain or side chain of each structural unit. For example, a copolymer of (meth) acrylic acid ester and (meth) acrylic acid can be used. In this case, carboxy groups are introduced depending on the proportion of acrylic acid. Moreover, the copolymer etc. of (meth) acrylic acid ester and acid phosphoxy and (meth) acrylate can be mentioned. In this case, a phosphate group is introduced.
Moreover, as an acidic group, the oligomer or polymer may be introduce | transduced into phosphoric acid ester. In this case, a phosphate group is introduced according to the position and ratio of the hydroxyl group. In the case of having hydroxyl groups at both ends of the oligomer or polymer, phosphate groups are introduced at both ends of the oligomer or polymer to have a total of two phosphate groups.
When the acidic 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.

  Specific examples of the oligomer or polymer as the acidic compound include, for example, polyoxyalkyl phosphate esters such as polyoxyethylene alkyl phosphate esters, polyoxyethylene polyoxypropylene phosphate esters, and polyether polyester phosphate esters. Examples thereof include phosphoric acid ester compounds; alkylpolyphosphonic acids; carboxy group-containing (meth) acrylic polymers. These may be used alone or in combination of two or more.

  As the acidic compound, a low molecular compound such as phosphate ester, sulfate ester, 1-hydroxyethane-1,1-diphosphonic acid may be used.

  The acidic compound preferably has an acid value. The acid value of the acidic compound is preferably 30 KOH mg / g or more, more preferably 60 KOH mg / g or more, and still more preferably 90 KOH mg / g or more.

  Here, the acid value is the number of milligrams of potassium hydroxide required to neutralize all acidic components in 1 g of the nonvolatile content. The same applies hereinafter.

  Among them, a liquid organic compound having at least one of a phosphoric acid group, a phosphonic acid group, a phosphoric ester group and a carboxy group having an acid value of 30 KOHmg / g or more is preferable, and a phosphoric acid group is particularly preferable. Moreover, what has a phosphate group in the both ends of an acidic compound is still more preferable.

  Among the commercially available products, those that can be used as acidic compounds include, for example, “DISPERBYK102, 110, 111” (all trade names) manufactured by Big Chemie Japan, “TEGODisper655” manufactured by Sakai Kogyo, and EFKA “Efca 6230” manufactured by Kirest Co., Ltd., “PH-210” manufactured by Kyrest Co., Ltd., “ARUFON UC3510” manufactured by Toagosei Co., Ltd., “CM292P” manufactured by Unichemical Co., Ltd., and the like.

“DISPERBYK111” is a phosphate ester compound of a block copolymer of ethylene glycol and polycaprolactone, and has phosphate groups at both ends of the copolymer.
“CN294P” is a phosphate ester compound of a block copolymer of ethylene oxide and propylene oxide, and has phosphate groups at both ends of the copolymer.
“ARUFON UC3510” is a copolymer of acrylic acid ester and acrylic acid, and has a plurality of carboxy groups.
“Cyrest PH210” is 1-hydroxyethane-1,1-diphosphonic acid, which is a low molecular weight compound having two phosphonic acid groups.

  It is preferable that an acidic compound is mix | blended with 0.1-50 mass% with respect to the whole colored resin particle, More preferably, it is 1-40 mass%. 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 polyester polyols 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. The average particle diameter of the colored resin particles may be adjusted as appropriate according to the type of the recording medium. For example, to improve the color development of the printed material using the coated paper, or to suppress the back-through of the printed material using the plain paper The average particle diameter is preferably about 100 nm to 250 nm. Here, the average particle diameter of the colored resin particles is a volume-based average particle diameter based on a dynamic light scattering method. As an example, a dynamic light scattering particle size distribution measuring apparatus “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 manufacture stage 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, and a phase containing at least a polyvinyl acetal resin, a coloring material, an acidic 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 a dispersed phase, It is possible to obtain an oil-in-oil (O / O) type emulsion by mixing the phases and removing the solvent B from the dispersed phase by reducing the pressure and / or heating.

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.

"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 .; carbon in one molecule such as isononanoic acid, isomyristic acid, hexadecanoic acid, isopalmitic acid, oleic acid, isostearic acid 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 acidic 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 exerted more when printed on a hardly permeable paper such as a 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 acidic compound and the solvent A, the range of the following ΔHSP value is preferably 14 to 25.
ΔHSP ² = (δd _{acidic compound-} δd _{solvent A} ) ² + (δp _{acidic compound-} δp _{solvent A} ) ² + (δh _{acidic 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 a dispersant having a basic group. As the basic dispersant, the solubility in the solvent A is preferably higher than that in the solvent B.

  Preferably, the basic dispersant has a solubility in the solvent B of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less. Preferably, the basic dispersant has a solubility in the solvent A of 3 g / 100 g or more at 23 ° C., more preferably 5 g / 100 g or more. More preferably, the basic dispersant is used so that the basic dispersant is substantially completely dissolved in the solvent A and the basic dispersant is not substantially dissolved in the solvent B at the mixing ratio of the water-in-oil emulsion. Selected.

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.
Moreover, it is preferable that the ORP value is 0 or less when 5.0% by mass of the basic dispersant is dissolved in dodecane.

  On the other hand, when the basic dispersant contains an acidic group together with the basic group, the basic dispersant is preferably used as a basic dispersant even if the acidic group is contained within the range in which the ORP value tends to be low. be able to. 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 and a pyridyl group. Among them, 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, an amide bond, etc. can be mentioned. Further, a nitrogen-containing structural unit such as a urethane bond or an amide 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),
"DISPERKBYK116, 2096, 2163" (all trade names) manufactured by Big Chemie Japan,
“Acetamine 24, 86 (alkylamine salt type)” (both trade names) manufactured by Kao Corporation,
“Disparon KS-860, KS-873N4 (amine salt of polymer polyester)” (both are trade names) manufactured by Enomoto Kasei Co., Ltd. can be used.

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 oil-in-oil type 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 example, the amino group is a group represented by the general formula —NR ¹ R ² , and R ¹ and R ² are each independently hydrogen, a hydrocarbon group having 18 or less carbon atoms, or 8 carbon atoms. Groups such as the following alkanol groups 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 part serves as an adsorbing group on the interface of the oil-in-oil emulsion and an adsorbing group of the colored resin particles, and an alkyl group having 12 or more carbon atoms is a solvent. Affinity is exhibited, and the emulsification stability of the oil-in-oil emulsion and the dispersibility of the colored resin particles can be further enhanced.

  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 two hydroxy groups can be provided to promote the adsorption to the interface of the oil-in-oil emulsion, the dioxygen-dioxide represented by the general formula (HOR) ₂ NH (R is a divalent hydrocarbon group) is used. Alkanolamine (secondary alkanolamine) 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, the solvent B, a coloring material, a solid resin, and an acidic 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.

As other specific examples of the solvent B, acetone, methyl ethyl ketone, ethyl acetate, and the like can be given. Further, those satisfying the relationship with the solvent A, the basic dispersant, and the resin can be appropriately selected and used. Can do.
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 more, more preferably 20 ° C. or more, and further preferably 50 ° C. or more. 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 may be either a dye or a pigment, and may be used in combination.

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

  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. More preferred are metal complex dyes.

  Examples of such oil-soluble dyes include OILBlue 613, OILYellow 107, SpiritBlackAB, and ROB-B of “OIL COLOR series” manufactured by Orient Chemical Industry Co., Ltd.

Examples of the metal complex dye include, for example, “VALIFAST COLOR series” manufactured by Orient Chemical Industry Co., Ltd., “ValifastBlack 3804, 3810 (solvent black 29), 3820, 3830, 3840 (solvent black 27), 3870, VarifastBlue 1605, 2606, 2620, 2670, VarianceOrange 3209, 3210, VariFastPink 2310N, 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. .

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.

  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.

  The average particle diameter of the pigment is preferably 300 nm or less, more preferably 150 nm or less. As a result, the dispersibility of the pigment in the dispersed phase can be kept good, and the final colored resin particle size can be made appropriate.

  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 solid resin can be improved, and the fixability 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 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.

  When a pigment is used for the color material, a pigment dispersant may be included in the dispersed phase in order to stably disperse the pigment in the dispersed phase, that is, the solvent B.

  Examples of the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, and a high molecular weight unsaturated acid. Ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalenesulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonylphenyl ether, polyester polyamine, Stearylamine acetate and the like can be used, and among them, the use of a polymer dispersant is preferable. These may be used alone or in combination of two or more.

  The blending amount of the pigment dispersant in the dispersed phase can be appropriately set, but from the viewpoint of pigment dispersibility, the mass ratio is preferably about 0.05 to 1.0 part with respect to 1 part of the pigment, and 1 to 1.0 part is more preferable.

As solid resin, it is 1 or more types among (1) polyvinyl acetal resin whose acetyl group is 10 mol% or less, (2) alkylphenol resin, and (3) ketone resin. Details are as described above. 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 solid resin in the solvent B is preferably 10 g / 100 g or more at 23 ° C., more preferably 20 g / 100 g or more. The solubility of the solid resin 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 solid resin is substantially completely dissolved in the solvent B and not substantially dissolved in the solvent A in the blending ratio of the oil-in-oil emulsion.

  The solid resin preferably has a solubility in water of 3 g / 100 g or less at 23 ° C., more preferably 0.5 g / 100 g or less, and still more preferably substantially does not dissolve. As a result, the water resistance of the solid resin itself is increased, whereby the water resistance of the dispersion is also increased, and the water resistance of the printed image can be increased.

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 acidic compound is a liquid organic compound having an acidic group. Details are as described above.
By adding an acidic compound, the color developability and abrasion resistance of the printed matter can be further improved. This is because it is possible to mix the colorant and the solid resin more uniformly and stably by the acidic compound.
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 acidic compound together with this solid resin, the wear resistance is improved as well as the water resistance. Can be made.
Moreover, an acidic compound can improve the stability of an oil-in-oil emulsion more in the manufacturing process of a colored resin particle dispersion.

  The acidic compound is not particularly limited, but preferably has higher solubility in the solvent B than the solvent A. The solubility of the acidic compound in the solvent B is preferably 1 g / 100 g or more at 23 ° C., more preferably 2 g / 100 g or more. Moreover, it is preferable that the solubility with respect to the solvent A of an acidic compound is 3 g / 100g or less at 23 degreeC, More preferably, it is 1 g / 100g or less, More preferably, it is 0.5 g / 100g or less. More preferably, the acidic compound is substantially completely dissolved in the solvent B and not substantially dissolved in the solvent A in the blending ratio of the oil-in-oil emulsion.

The content of the acidic 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 acidic 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 mass ratio of the acidic compound to the color material is preferably (acid compound mass) / (color 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.

  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.

  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 desirably 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 acidic compound and a non-aqueous solvent (solvent B). A dispersed phase is used as a phase, and a continuous phase and a dispersed phase are mixed to prepare an oil-in-oil (O / O) type pre-emulsion. 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 color material may agglomerate by acting with other components, particularly an acidic compound. However, according to this two-stage emulsification method, the color material can be added 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 acidic 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 acidic compound, it is possible to control the average particle diameter of the colored resin particles 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 for ink jet printing, offset printing, stencil printing, gravure printing, electrophotographic printing, and the like. In particular, since the dispersion stability is good, it is preferably used as an inkjet ink.

  When used as an inkjet ink, it is possible to use the colored resin particle dispersion as it is, and if necessary, various additives that are 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, it is preferably 5 to 30 mPa · s at 23 ° C., and preferably 5 to 15 mPa · s. More preferably, 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.

<Ink preparation>
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, since the volatile component is contained in the acidic compound, the nonvolatile component amount is shown together with the total amount of the acidic compound in parentheses (the same applies to Tables 5 and 6 described later).

  A continuous phase was prepared by mixing the solvent A and the basic dispersant shown in each table in each compounding amount. Next, the solvent B shown in each table, a dye, and a solid resin were mixed in each blending amount, and then an acidic compound was added to adjust the dispersed phase.

  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.

  While the obtained emulsion was decompressed with an evaporator, the solvent B in the dispersed phase was removed to obtain a colored resin particle dispersion. The removal rate of the solvent B was almost 100% by mass. This colored fine particle dispersion was used as an ink as it was.

  Tables 5 and 6 show the ink formulations of Examples and Comparative Examples after removal of solvent B. From the total amount of solids (basic dispersant, dye, acidic compound, solid resin) relative to the total amount of ink, the amount of solids is determined and shown in each table.

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

(Dispersed phase)
Methanol: C1-C1 alcohol solvent, manufactured by Wako Pure Chemical Industries, Ltd.
Valifast Black 3810: Black metal complex dye, “Valifast Black 3810” manufactured by Orient Chemical Industries, Ltd.
BYK-111: Liquid organic compound having two phosphate groups (phosphate ester compound having phosphate groups at both ends of the copolymer) Copolymer (acid phosphate ester) having acidic groups, Big Chemie Japan Co., Ltd. “DISPERBYK-111” manufactured by company, acid value 129 KOH mg / g, non-volatile content 95.0%.

  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.
The dyes were dissolved in the solvent B at the blending ratios of the dispersed phases shown in Table 2 and Table 3, respectively, and the solubility in the solvent A was less than 0.5 g / 100 g at 23 ° C.
The solid resin is dissolved in the solvent B in the proportions of the dispersed phases shown in Table 2 and Table 3, respectively, 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 acidic compound was dissolved in the solvent B at the mixing ratio of the dispersed phases shown in Tables 2 and 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).
Various solid resins: 22 to 27 (δd = 12 to 20, δp = 5 to 12, δh = 10 to 20).
Various acidic compounds: 22 to 27 (δd = 12 to 20, δp = 5 to 12, δh = 10 to 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.
DISPERBYK-111: The ORP value when dissolved by 5.0% by mass is higher than the ORP value when dissolved by 0.5% by mass in methanol, and the ORP when dissolved by 5.0% by mass in methanol The value was 350.

(Solid resin in dispersed phase)
Details of the solid resin in the dispersed phase are shown in Table 4.
The polyvinyl butyral resin (butyral resin) used in the examples is manufactured by Sekisui Chemical Co., Ltd., and the alkylphenol resins and ketone resins used in the examples are manufactured by Arakawa Chemical Industries, Ltd. Moreover, all the polyvinyl alcohol used by the comparative example is a product made from Nippon Vineyard-Poval Co., Ltd., and the polyvinyl acetate used by the comparative example is a product made by Nippon Synthetic Chemical Industry Co., Ltd.

<Evaluation>
The following evaluation was performed using each of the inks described above. The results are shown in each table.

(Abrasion resistance)
Each of the inks described above is loaded into a line-type ink-jet printer “Olfis X9050” (manufactured by Riso Kagaku Co., Ltd.), and a solid image is printed on high-quality coated paper “Aurora Coat” (manufactured 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 above-mentioned scratch resistance. After printing for 24 hours, draw a line on the characters on the coated paper printing part 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.

(Storage stability)
Ink was put into a predetermined glass bottle, sealed, and stored in a constant temperature bath at 70 ° C. Two weeks after storage, the presence or absence of precipitation was visually observed and evaluated according to the following criteria.
A: There is no precipitation.
B: There is a small amount of fluid precipitate.
C: There is a non-flowable precipitate.

(Odor)
Ink was put into a predetermined glass bottle, sealed, and stored in a constant temperature bath at 70 ° C. After 2 weeks of storage, a sensory evaluation was made as to whether or not there was a specific odor, and the following criteria were used. The sensory evaluation was carried out by 5 panelists and averaged.
A: There is no acetic acid odor.
B: There is a little acetic acid odor.
C: There is an acetic acid odor.

(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 above tables, the inks of the examples had good scratch resistance, water resistance and marker resistance. Moreover, the ink of each Example was excellent in storage stability and was able to suppress odor. Moreover, the average particle diameter of the colored resin particles was also in an appropriate range.
In the inks of Examples 1 to 6, the solid resin had a mass average molecular weight of 60000 or less, and was excellent in storage stability. Further, in the inks of Examples 1 to 4, since the mass average molecular weight of the solid resin was 30000 or less, the storage stability was further improved.
In Examples 8 and 9, an alkylphenol resin and a ketone resin were used, and good results were obtained as well as the butyral resin.

In the inks of Comparative Examples 1 to 3, polyvinyl alcohol was used, and odor became a problem.
In the ink of Comparative Example 4, polyvinyl acetate was used, and odor became a problem. In addition, the scratch resistance decreased.

Claims (6)

Colored resin particles containing a coloring material, a solid resin, and a liquid organic compound having an acidic group, a basic dispersant, and a non-aqueous solvent,
The colored resin particle dispersion, wherein the solid resin contains at least one of (1) a polyvinyl acetal resin having an acetyl group of 10 mol% or less, (2) an alkylphenol resin, and (3) a ketone resin.   The colored resin particle dispersion according to claim 1, wherein (1) the polyvinyl acetal resin includes a polyvinyl butyral resin having a hydroxyl group of 20 to 50 mol% and an acetalization degree of 50 to 80 mol%.   The colored resin particle dispersion according to claim 1 or 2, wherein the (1) polyvinyl acetal resin has a mass average molecular weight of 60000 or less.   The colored resin particle dispersion according to any one of claims 1 to 3, wherein the acidic group of the liquid organic compound having an acidic group contains a phosphoric acid group. 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,
An oil obtained by dispersing a dispersed phase containing the non-aqueous solvent B, the coloring material, the solid resin, and the liquid organic compound having an acidic group in a continuous phase containing the non-aqueous solvent A and the basic dispersant. Make a middle oil type 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 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.