JP2014201731A - Dispersion of resin fine particle, dispersion of resin fine particle including color material, and inkjet ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersion of a resin fine particle and a dispersion of a resin fine particle including a color material which allows preparation of an inkjet ink capable of achieving excellent discharge stability and a high bleed-suppressing effect at the same time.SOLUTION: A dispersion of a resin fine particle is obtained by polymerizing an α,β-unsaturated hydrophobic compound in a dispersion liquid containing the α,β-unsaturated hydrophobic compound, a compound of formula (1) and a water-soluble resin of an acid number of 80-315. (1) R-O-(CHCHO)-(CO)-(R)-X, where Ris an 8-18C alkyl or aryl group; Ris a 1-5C alkylene group; X is an anionic group; k is an integer of 30-150; l is 0 or 1; and n is an arbitrary integer of 1 or greater.

Description

  The present invention relates to a resin fine particle dispersion and a coloring material-containing resin fine particle dispersion. Further, the present invention relates to an ink jet ink containing the resin fine particle dispersion and the coloring material-containing resin fine particle dispersion.

  Ink-jet inks are required to have various properties such as high ejection stability, gloss of recorded matter, scratch resistance, curl suppression, and color mixing between different colors (bleed). In recent years, a wide variety of ink jet ink production methods have been proposed to satisfy these characteristics. Among them, a method for obtaining a colored fine particle dispersion containing a coloring material and a resin by emulsion polymerization can be mentioned as one of typical methods for producing an inkjet ink.

  Emulsion polymerization is a production method in which a hydrophobic monomer is emulsified in water with a surfactant and polymerized. Furthermore, it has been studied to produce fine particles encapsulating a coloring material by previously dissolving an oily dye in the hydrophobic monomer. Non-Patent Document 1 discloses a resin fine particle dispersion obtained by using styrene as a monomer and using polyoxyethylene alkyl ether as a surfactant. Similarly, Patent Document 1 discloses fine color material-containing resin fine particles made of polyoxyethylene alkyl ether.

On the other hand, Patent Document 2 describes an ink composition having excellent scratch resistance and water resistance. The ink composition includes at least a colorant, polymer fine particles, a water-soluble organic solvent, and water. The polymer fine particles have a film-forming property and have a carboxyl group on the surface thereof. When the polymer fine particles are brought into contact with 3 volumes of an aqueous emulsion of 0.1% by weight and 1 volume of a divalent metal salt aqueous solution having a concentration of 1 mol / l, the light transmittance at a wavelength of 700 nm is an initial value of 50. The reactivity with the divalent metal salt is such that the time when the percentage is 1 × 10 ⁴ seconds or less. Further, Patent Document 3 discloses a method for introducing a carboxyl group into the surface of polymer fine particles by emulsion polymerization using a fatty acid salt such as fatty acid sodium.

US Pat. No. 7,544,418 JP 2000-272220 A JP 2007-332286 A

“Minimalization polymerisation: Applications and Materials”, Macromolecular Symposia, 2000, Vol. 151, No. 1, p. 549-555

  The present inventors use polyoxyethylene alkyl ether described in Non-Patent Document 1 and Patent Document 1 as a surfactant during emulsion polymerization, and use the resulting resin fine particle dispersion for the preparation of ink jet ink. Using. As a result, it was confirmed that excellent discharge stability was obtained. Specifically, the above-described ink is stable even when the discharge frequency is increased, and the ink is excellent without decreasing the discharge speed. In addition, due to the steric repulsion of long-chain water-soluble polyoxyethylene, aggregation of resin fine particles is suppressed, and excellent dispersion stability is exhibited. When used as an inkjet ink, the resulting ink has good ejection properties. is there. However, since there are no reactive groups with the polyvalent metal salt or the like on the surface of the resin fine particles, there is no bleed suppressing effect on the paper surface, and the print quality of color images and the like was not satisfactory.

  In addition, the present inventors obtained a resin fine particle dispersion and a colorant-encapsulating resin fine particle dispersion using the styrene-acrylic acid copolymer disclosed in Patent Document 2 as a dispersant. The properties of the ink-jet ink contained were similarly examined. Further, the dispersion of resin fine particles having a carboxyl group introduced into the surface with a fatty acid salt as disclosed in Patent Document 3 was also used as an inkjet ink, and the properties of the ink were similarly examined. As a result, these inks showed an excellent bleeding suppression effect. This excellent bleed suppression effect is based on a mechanism in which polyvalent metal salts and the like in the reaction solution associate with acrylic acid as a surfactant and the resin fine particles aggregate on the paper surface. However, these inks cannot achieve satisfactory ejection stability by an ink jet recording method in which droplets are ejected by thermal energy. Specifically, problems such as a decrease in discharge frequency, a decrease in discharge speed, and landing deviation on the paper surface occurred.

  The present invention has been made in view of such problems of the prior art. That is, an object of the present invention is to provide a resin fine particle dispersion and a colorant-encapsulating resin fine particle dispersion capable of preparing an inkjet ink that can simultaneously achieve excellent ejection stability and a high bleeding suppression effect. There is to do.

The above object can be achieved by the following invention. That is, according to the present invention, in a dispersion containing an α, β-unsaturated hydrophobic compound, a compound represented by the following general formula (1), and a water-soluble resin having an acid value of 80 or more and 315 or less. A resin fine particle dispersion obtained by polymerizing the α, β-unsaturated hydrophobic compound is provided.
General formula (1)
^{_{R 1 -O- (CH 2 CH 2}} O) k - (CO) l - (R 2) m -X n
(In the formula, R ¹ represents an alkyl group or an aryl group having 8 to 18 carbon atoms, R ² represents an alkylene group having 1 to 5 carbon atoms, X represents an anionic group, k is An integer of 30 or more and 150 or less, l represents 0 or 1, m represents 0 or 1, and n represents an arbitrary integer of 1 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the resin fine particle dispersion and the color material inclusion resin fine particle dispersion which can adjust the inkjet ink which can achieve the outstanding discharge stability and the high suppression effect of bleeding simultaneously are provided.

Hereinafter, the present invention will be described in more detail.
The present inventors perform polymerization in order to obtain a resin fine particle dispersion and a colorant-encapsulating resin fine particle dispersion capable of preparing an ink jet ink that can achieve both excellent ejection stability and a high bleeding suppression effect. The method and the surfactant used in the polymerization were investigated. As a result, in the dispersion containing the α, β-unsaturated hydrophobic compound, the compound represented by the following general formula (1), and a water-soluble resin having an acid value of 80 or more and 315 or less, the α, β -It has been found that a resin fine particle dispersion obtained by polymerizing an unsaturated hydrophobic compound can provide an ink excellent in ejection stability and bleeding suppression effect when used in the preparation of an inkjet ink. The present inventors also include an α, β-unsaturated hydrophobic compound, a compound represented by the following general formula (1), a water-soluble resin having an acid value of 80 or more and 315 or less, and a coloring material. When the colorant-containing resin fine particle dispersion obtained by polymerizing the α, β-unsaturated hydrophobic compound in the dispersion is used for the preparation of an inkjet ink, it has excellent ejection stability and bleed suppression effect. It was found that the ink can be prepared.

General formula (1)
^{_{R 1 -O- (CH 2 CH 2}} O) k - (CO) l - (R 2) m -X n
(In the formula, R ¹ represents an alkyl group or an aryl group having 8 to 18 carbon atoms, R ² represents an alkylene group having 1 to 5 carbon atoms, X represents an anionic group, k is An integer of 30 or more and 150 or less, l represents 0 or 1, m represents 0 or 1, and n represents an arbitrary integer of 1 or more.

The inventors presume why the inkjet ink prepared using the resin fine particle dispersion and the colorant-encapsulating resin fine particle dispersion can simultaneously exhibit excellent ejection stability and high bleeding suppression effect as follows. doing. R ¹ in the general formula (1) is adsorbed to an α, β-unsaturated hydrophobic compound as a raw material of resin fine particles or colorant-containing resin fine particles described later in the dispersion before polymerization, and resin fine particles after polymerization. Alternatively, it is a segment having a function of adsorbing to the coloring material-containing resin fine particles. Also, the compound of general formula (1) contains 30 to 150 units of oxyethylene. This long-chain oxyethylene is a segment exhibiting water-solubility, and it is considered that the bulky long-chain oxyethylene is oriented from the surface of the resin fine particles or color material-containing resin fine particles obtained by polymerization toward the aqueous phase. It is considered that the steric repulsion of the oxyethylene chain exhibits a function of preventing aggregation of resin fine particles or coloring material-containing resin fine particles statically and dynamically. X _n in the general formula (1) is located in the outermost shell of the resin fine particles or the color material-encapsulating resin fine particles, and reacts with the reactant when applied to the recording medium as ink, so that the resin fine particles or the color material This is a segment serving as a reaction base point for inducing aggregation of the contained resin fine particles.

That is, the resin fine particles and the colorant-containing resin fine particles in the dispersion of the present invention are adsorbed with the polymer of the general formula (1) and the polymer of α, β-unsaturated hydrophobic compound at the R ¹ segment. The oxyethylene chain in the compound of the general formula (1) expresses steric repulsion between the resin fine particles or between the colorant-containing resin fine particles, and the X _n segment located at the molecular end has high reactivity. Since such fine particles are contained, the resin fine particle dispersion and the colorant-containing resin fine particle dispersion of the present invention can exhibit excellent ejection stability and a high bleed suppression effect when applied as an ink jet ink.

  In addition, the water-soluble resin having an acid value of 80 or more and 315 or less used in the present invention has a higher density of reactive base points per molecule than the compound represented by the general formula (1). The reactivity of the obtained resin fine particles or color material-containing resin fine particles is increased. Therefore, in addition to the compound of the general formula (1), the reactivity of the resin fine particle dispersion or the colorant-encapsulating resin fine particles obtained by using a surfactant which is a water-soluble resin having an acid value of 80 or more and 315 or less is used. Can be controlled.

[Resin fine particle dispersion]
Next, the constituent elements and manufacturing process of the resin fine particle dispersion of the present invention will be described in detail. In the present invention, “CMC” of a compound or water-soluble resin means “critical micelle concentration” for a compound having properties as a surfactant. In the present invention, “(meth) acrylate” means both “acrylate” and “methacrylate”, and “(meth) acryl” means both “acryl” and “methacryl”.

(Α, β-unsaturated hydrophobic compounds)
The “α, β-unsaturated hydrophobic compound” in the present invention means an α, β-unsaturated compound and a hydrophobic compound. The “α, β-unsaturated compound” means a compound having an unsaturated bond (such as C═C) between the α-position carbon and the β-position carbon. Furthermore, the “hydrophobic compound” means a compound having no hydrophilic group (for example, acidic group, basic group, hydroxy group, alkylene oxide group, etc.). Specific examples of the α, β-unsaturated hydrophobic compound include aromatic vinyl compounds such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- Propyl (meth) acrylate, i-butyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, Examples include (meth) acrylic acid alkyl esters such as cyclohexyl (meth) acrylate and hexadecyl (meth) acrylate; ethylene and the like.
Properties required for the α, β-unsaturated hydrophobic compound used in the present invention include polymerization rate and polymerization conversion. Moreover, as a resin characteristic after superposition | polymerization, affinity with a glass transition temperature and a coloring material is mentioned. In order to adjust these characteristics, two or more kinds of α, β-unsaturated hydrophobic compounds can be used.

  Moreover, the range which does not break the emulsification state of the dispersion liquid which contains the compound represented by the (alpha), (beta)-unsaturated hydrophobic compound and the following general formula (1) mentioned later, and an acid value 80-315 below. It is also possible to polymerize by adding an appropriate amount of α, β-unsaturated hydrophilic compound. Specific examples of the α, β-unsaturated hydrophilic compound include hydrophilic polymerizable monomers such as acrylic acid, methacrylic acid, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinyl imidazole, and maleic acid derivatives.

(Compound represented by the general formula (1))
In the present invention, a dispersion of the above α, β-unsaturated hydrophobic compound using both the compound represented by the following general formula (1) and a water-soluble resin having an acid value of 80 or more and 315 or less as a surfactant. In this dispersion, an α, β-unsaturated hydrophobic compound is emulsion-polymerized.
General formula (1)
^{_{R 1 -O- (CH 2 CH 2}} O) k - (CO) l - (R 2) m -X n
(In the formula, R ¹ represents an alkyl group or an aryl group having 8 to 18 carbon atoms, R ² represents an alkylene group having 1 to 5 carbon atoms, X represents an anionic group, k is An integer of 30 or more and 150 or less, l represents 0 or 1, m represents 0 or 1, and n represents an arbitrary integer of 1 or more.

In the general formula (1), examples of the alkyl group represented by R ¹ include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group (cetyl group). , Heptadecyl group, octadecyl group and the like. These alkyl groups may have any of linear, branched, and cyclic structures. Examples of the aryl group include octylphenyl group, nonylphenyl group, decylphenyl group, xylyl group and the like.

The R ¹ —O— (CH ₂ CH ₂ O) _k portion of the compound represented by the general formula (1) can be synthesized by a condensation reaction between an alcohol represented by R ¹ —OH and ethylene oxide. it can. The repeating number k of the oxyethylene group (CH ₂ CH ₂ O) can be controlled by the charging ratio of the alcohol represented by R ¹ —OH and ethylene oxide, and k may be from 30 to 150, more preferably 50. The range is 100 or less.

In formula (1), as an example of the anionic group represented by X, an anionic group selected from the group consisting of —COOM, —SO ₃ M, —PO ₃ HM, —PO ₃ M ₂ and —SO ₂ NH ₂ Groups, and in the above formulas, M represents a hydrogen atom or an alkali metal. n is an arbitrary integer of 1 or more, and typically n = 1.

As an example of a method for producing the compound represented by the formula (1), first, R ¹ —O— (CH ₂ CH ₂ O) _k —H described above is synthesized, and acrylonitrile is added to the terminal OH group of this formula. Then, it is oxidized to add a carboxylic acid. Further, there may be mentioned a method of directly oxidizing terminal —CH ₂ CH ₂ OH with a platinum catalyst or the like, and a method of reacting sodium monochloroacetate after the terminal —CH ₂ CH ₂ OH is converted to an alcoholate with an alkali. Among these methods, industrial reaction with sodium monochloroacetate is advantageous.

The reaction with sodium monochloroacetate, the general formula (1) represented by compounds _{- (CO) l - (R} 2) portion of _m -X _n is -CH ₂ COONa ^{next, l = 0, R 2 =} CH 2 , M = 1, X = COONa, n = 1.
In general formula (1), when l = 1, an ester bond is present. Examples of the method for producing such a compound include a reaction in which an acid anhydride is half-esterified to the hydroxyl group at the terminal of the above-mentioned R ¹ —O— (CH ₂ CH ₂ O) _k —H. Examples of acid anhydrides include succinic anhydride. In the reaction using succinic anhydride, the — (CO) ₁ — (R ² ) _m —X _n moiety of the compound represented by the general formula (1) is —CO—CH ₂ —COONa, where l = 1. R ² = CH ₂ , m = 1, X = COONa, n = 1.

Further, phosphorus oxychloride may be condensed and dehydrated to the terminal hydroxyl group of the above-mentioned R ¹ —O— (CH ₂ CH ₂ O) _k —H. In this reaction, the moiety of — (CO) ₁ — (R ² ) _m —X _n of the compound represented by the general formula (1) becomes —PO (OH) (ONa), and l = 0, m = 0, X = PO (OH) (ONa), n = 1.

(Water-soluble resin)
Next, a water-soluble resin having an acid value of 80 to 315, which is a surfactant, will be described.
The water-soluble resin, which is an essential component of the present invention, is a vinyl copolymer obtained by copolymerizing at least one α, β-unsaturated hydrophobic compound and at least one α, β-unsaturated hydrophilic compound. A polymer is preferred.

  As the α, β-unsaturated hydrophobic compound, the same compound as represented by the general formula (1) can be used. For example, styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, vinyl naphthalene, 4-vinyl benzoate Vinyl monomers having an aromatic functional group such as acid, esterified vinyl benzoic acid, N-vinylcarbazole, etc .; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid esters such as cyclohexyl acid; acrylamide monomers such as N-methylol (meth) acrylamide and N, N-dimethylaminopropyl (meth) acrylamide; N-vinylacetamide, N-vinylformamide and the like.

  Examples of α, β-unsaturated hydrophilic compounds include acrylic acid, methacrylic acid, acrylamide, acrylonitrile, vinyl ether, vinyl acetate, vinyl imidazole, ethylene, maleic acid derivatives and the like.

The acid value is represented by the number of mg of potassium hydroxide required to neutralize the acidic component in 1 g of resin. The hydrophilic resin used in the present invention preferably has a stable dissolved state when dissolved in water in which the base is dissolved, in addition to having an acid value of 80 or more and 315 or less. A resin having an acid value of greater than 315 is not preferable because it has high water solubility and the surface activity is reduced. On the other hand, a resin having an acid value of less than 80 is not preferable because it has high hydrophobicity and low solubility in water.
The acid value can be calculated and the theoretical acid value can be calculated if the monomer component ratio in the resin is known. Further, when the monomer component ratio in the resin is not known, it can be experimentally determined from neutralization measurement.

(Mass ratio between the compound represented by the general formula (1) and the water-soluble resin)
The mass ratio of the compound represented by the general formula (1) constituting the resin fine particle dispersion of the present invention to the water-soluble resin is preferably in the range of 30:70 to 85:15, more preferably 50. : 50 or more and 70:30 or less.
When the amount of the compound of the general formula (1) is more than 85 parts by mass with respect to 15 parts by mass of the water-soluble resin, when the obtained resin fine particle dispersion is used as an inkjet ink, the ejection stability is excellent, but the reactive group is insufficient. As a result, the cohesiveness is lowered, and the suppression of bleeding may be insufficient.
On the contrary, when the amount of the compound of the general formula (1) is less than 30 parts by mass with respect to 70 parts by mass of the water-soluble resin, the number of reactive groups in the resulting resin fine particle dispersion increases. Although the bleed suppressing effect is high, the ejection stability may be insufficient.

  Mass ratio of total amount (X) of compound represented by general formula (1) and water-soluble resin in dispersion and amount (Y) of polymerizable monomer containing α, β-unsaturated hydrophobic compound X: Y is preferably 1: 100 or more and 50: 100 or less. If the mass ratio of X: Y is within this range, the α, β-unsaturated hydrophobic compound can be reliably emulsified with the compound represented by the general formula (1) and the water-soluble resin, and the yield of emulsion polymerization Can be kept high.

[Polymerization process]
(Preparation of dispersion)
In the present invention, prior to the polymerization of the α, β-unsaturated hydrophobic compound, the α, β-unsaturated hydrophobic compound is converted into a compound represented by the general formula (1) and a water-soluble acid value of 80 or more and 315 or less. Disperse with a resin to obtain a dispersion. As a method for obtaining the dispersion, various known means can be used. Among them, it is preferable to use a stirrer having a high shear stress or ultrasonic irradiation having a cavitation effect. Specific examples include the following methods. A water-soluble resin having a general formula (1) and an acid value of 80 or more and 315 or less is dissolved in water to obtain an aqueous solution, and then an α, β-unsaturated hydrophobic compound is dropped little by little, and mechanical stirring is performed 1 Do more than an hour. Then, it is preferable to disperse | distribute until it becomes a desired particle size by ultrasonic irradiation. The particle size can be controlled by the amount of the compound of the general formula (1) and the water-soluble resin having an acid value of 80 or more and 315 or less.

The content of the compound of the general formula (1) and the water-soluble resin in the aqueous solution is preferably in the range of 1 to 100 times that of CMC. When it is less than 1 time of CMC, the dispersion of the α, β-unsaturated hydrophobic compound becomes insufficient, causing problems such as an increase in the average particle size in the dispersion and a wide particle size distribution. Further, the monomer of the α, β-unsaturated hydrophobic compound that has not been emulsified may be polymerized as coarse particles, and precipitation may occur as a water-insoluble resin that cannot be dispersed. On the other hand, when the compound of the general formula (1) and the water-soluble resin are contained more than 100 times the CMC, in addition to being uneconomical, bleeding suppression of ink jet ink prepared using the obtained resin fine particle dispersion is suppressed. The effect may be reduced.
When adopting ultrasonic irradiation as the dispersion method, it is preferable to use ultrasonic waves having a frequency of 20 kHz to 850 kHz. In addition, it is preferable that the dispersion is prepared and the dispersion is irradiated with ultrasonic waves for 1 minute to 10 hours.

(Polymerization process)
The resin fine particle dispersion of the present invention is a dispersion containing an α, β-unsaturated hydrophobic compound, a compound represented by the general formula (1), and a water-soluble resin having an acid value of 80 or more and 315 or less. , Α, β-unsaturated hydrophobic compound. In this polymerization, the polymerization time can be shortened by adding a polymerization initiator to the dispersion. As a polymerization method, heat polymerization is generally used, but photopolymerization is also possible. In the case of heat polymerization, the reaction temperature is preferably from 40 to 100 degrees, and the reaction time is preferably from 1 to 50 hours.

(Polymerization initiator)
In the aforementioned polymerization step, either a water-soluble polymerization initiator or an oil-soluble polymerization initiator can be used. Specific examples of the water-soluble polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; and peracid salts such as hydrogen peroxide. Specific examples of the oil-soluble polymerization initiator include 2,2′-azobis- (2-isobutyronitrile) and 2,2′-azobis- (2-methylbutyronitrile).
The concentration of the polymerization initiator is preferably 0.01% by mass or more and 10% by mass or less, and preferably 0.03% by mass or more and 5% by mass with respect to the total mass of the polymerizable monomer containing the α, β-unsaturated hydrophobic compound in the dispersion. The following is more preferable.

(Hydrohove)
When emulsion polymerization of a hydrophobic monomer is performed using oil droplets having a small particle size, there may be a problem of non-uniform particle size of monomer oil droplets containing the hydrophobic monomer. The monomer diffuses from the monomer oil droplets having a large specific surface area in water, and is absorbed by the oil droplets having a smaller specific surface area, that is, coarse monomer particles. This phenomenon is called Ostwald ripening, and the particle size of the monomer oil droplets becomes more uneven. In order to suppress this Ostwald ripening, it is known to add a water-insoluble compound having an affinity for a hydrophobic monomer. This compound is a hydrophobe.

In the present invention, after adding a hydrophobe to an α, β-unsaturated hydrophobic compound in advance, a dispersion is prepared using the compounds of the general formulas (1) and (2) and polymerized to obtain a particle size. A uniform resin fine particle dispersion can be obtained. Examples of hydrophobes that can be used in the present invention include hexadecane, dodecyl methacrylate, stearyl methacrylate, chlorobenzene, dodecyl mercaptan, olive oil, blue dye (solvent blue 70), and polymethyl methacrylate.
The amount of hydrophobe used in preparing the dispersion is preferably 0.01% by mass or more and 30% by mass or less based on the total mass of the polymerizable monomer containing the α, β-unsaturated hydrophobic compound. More preferably, the content is 1% by mass or more and 10% by mass or less.

(PH adjuster)
A pH adjuster may be added to the resin fine particle dispersion of the present invention and the dispersion during polymerization. Specific examples of the pH adjusting agent that can be used in the present invention include sodium hydrogen carbonate, sodium acetate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, 3- (N-morpholino) propanesulfonic acid, methyl-3- Aminopropanesulfonic acid, 2- (cyclohexylamino) ethanesulfonic acid, etc. are mentioned. The pH adjuster is preferably added so that the pH of the resin fine particle dispersion is in the range of 5.5 to 11.

(Additive)
When preparing an inkjet ink using the resin fine particle dispersion of the present invention, a hydrophilic organic solvent, a surfactant, a pH adjuster, a preservative, a water-soluble resin, and the like can be added as necessary. .

[Color material-containing resin fine particle dispersion]
The coloring material-containing resin fine particle dispersion of the present invention includes an α, β-unsaturated hydrophobic compound, a compound represented by the general formula (1), a water-soluble resin having an acid value of 80 to 315, and a coloring material. It is obtained by polymerizing an α, β-unsaturated hydrophobic compound in a dispersion containing Polymerization conditions, a polymerization initiator, additives for preparing an ink jet ink, and the like are the same as those in the above [resin fine particle dispersion], [polymerization step], and (additive).

(Color material)
The color material-encapsulating resin fine particles constituting the color material-encapsulating resin fine particle dispersion of the present invention have a structure in which a resin encapsulates the color material. Produced by dissolving the coloring material in the α, β-unsaturated hydrophobic compound in advance and then performing the polymerization reaction, or by adsorbing the α, β-unsaturated hydrophobic compound to the surface of the coloring material and then performing the polymerization reaction. it can. The content of the color material in the color material-encapsulating resin fine particle dispersion of the present invention is 0.4 to 20 times by mass with respect to the content of the polymer of the α, β-unsaturated hydrophobic compound. Preferably there is. When the content of the color material is within this range, when an ink-jet ink is prepared using the color material-encapsulating resin fine particle dispersion of the present invention, its storage stability, color developability and image density are excellent. When the content of the color material is less than 0.4 times the content of the polymer of the α, β-unsaturated hydrophobic compound, the color developability and the image density may be unsatisfactory. On the other hand, if the amount of the color material is more than 20 times, the glossiness and scratch resistance of the recorded matter may be lowered.

When an oily dye is used as the coloring material, the oily dye can be polymerized after being dissolved in the α, β-unsaturated hydrophobic compound. A detailed study of this polymerization method is reported in Colloid and Polymer Science, December 2003, Vol. 282, p119-126.
In addition, as a method for carrying out the polymerization reaction after adsorbing the α, β-unsaturated hydrophobic compound to the surface of the color material, the color material dispersion and the dispersion of the α, β-unsaturated hydrophobic compound are individually adjusted. And a method of polymerizing after mixing. Regarding this production method, “Encapsulation of Carbon Black by Miniemulsion Polymerization”, Macromolecular Chemistry and Physics, January 2001, vol. 202, p. Detailed studies are reported in 51-60.
Examples of the color material that can be used in the color material-containing resin fine particle dispersion of the present invention include carbon black, a color pigment, and an oily dye.

  Examples of the carbon black that can be used as the coloring material of the coloring material-containing resin fine particle dispersion of the present invention include carbon black such as gas black, furnace black, medium thermal carbon black, acetylene black, and ketjen black. Specific examples include Color Black FW series, Special Black series, High Black series, Printex (printex and above, manufactured by Degussa Japan). When carbon black is used as a coloring material, the surface thereof preferably has a high affinity for α, β-unsaturated hydrophobic compounds and hydrophobes. Specifically, it may be carbon black surface-modified with a functional group such as a carbonyl group or a phenolic hydroxyl group, carbon black surface-treated with a lactone or a carboxylic acid anhydride, or carbon black having a chromene structure on the surface. preferable. Moreover, the carbon black which surface-modified hydrophobic groups, such as an alkyl group and a phenyl group, may be sufficient.

(Color pigment)
Examples of color pigments that can be used as the colorant of the colorant-encapsulating resin fine particle dispersion of the present invention include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments ( Examples thereof include phthalocyanine pigments, perylene pigments, perinone pigments, thioindigo pigments, isoindolinone pigments and quinophthalone pigments), nitro pigments and nitroso pigments. The color pigment preferably has a high affinity for α, β-unsaturated hydrophobic compounds and hydrophobes as in the case of the carbon black described above.

(Oil-based dye)
Examples of oil-soluble dyes that can be used as the color material of the color material-containing resin fine particle dispersion of the present invention include black, yellow, magenta, and cyan dyes. For example, any oil-based dye may be used as long as it is described in the color index (COOLUR INDEX). In the present invention, a novel oily dye not described in the color index can also be used.
Specific examples of black oil-based dyes include Solvent Black 5 and CI Solvent Black 7 from Dystar. Cyan dyes include C.I. I. Solvent blue 33, 38, 42, 45, 53, 65, 67, 70, 104, 114, 115, 135 etc. are mentioned. As the magenta dye, C.I. I. Solvent Red 25, 31, 86, 92, 97, 118, 132, 160, 186, 187, 219 and the like. Examples of yellow dyes include C.I. I. Solvent Yellow 1, 49, 62, 74, 79, 82, 83, 89, 90, 120, 121, 151, 153, 154 and the like.

(Average particle size of fine particles)
The resin fine particles in the resin fine particle dispersion of the present invention and the color material-containing resin fine particles in the color material-containing resin fine particle dispersion preferably have an average particle size in the range of 10 nm to 500 nm, more preferably in the range of 50 nm to 300 nm. . The average particle diameter can be obtained by measuring the value of D ₅₀ , which is a volume average median diameter of resin fine particles or color material-containing resin fine particles, using a particle size analyzer such as “Microtrack UPA EX-150” manufactured by Nikkiso.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited by the following Example, unless the summary is exceeded. In the text, “parts” and “%” are based on mass unless otherwise specified.
First, a method for producing a surfactant and a dispersion will be described.

<Production of surfactant 1-1>
A reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol (a reagent manufactured by Wako Pure Chemical Industries) and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring while maintaining the pressure at 0.4 MPa and the temperature of 35 ° C., and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., and the volatilization loss was measured to determine the reaction rate of ethylene oxide. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 21.1 g was obtained.

Purified polyoxyethylene cetyl ether (21.1 g, 0.0073 mol) and sodium hydroxide (0.1 g) were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.85 g (0.0073 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours. After cooling, the solid in the reaction vessel was taken out on a filter paper. This was washed with cold ion-exchanged water, and purified polyoxyethylene cetyl ether represented by the structural formula of C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) _n —CH ₂ COONa (n is an integer of 1 or more). 14.6 g of sodium carboxylate (surfactant 1-1) was obtained.

<Surfactant 1-2>
50 g of methyl ethyl ketone (hereinafter referred to as MEK) as a solvent and 63 g of styrene, 25 g of butyl acrylate and 12 g of acrylic acid as monomers were prepared in a 300 ml flask. After raising the temperature to 75 ° C. with stirring under a nitrogen stream, 1 g of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator to initiate polymerization, and the reaction was further continued for 7 hours. . After the reaction, the flask was cooled and diluted with 100 ml of MEK. As a result of charging this reaction liquid into hexane, a white product was obtained. The monomer ratio at the time of synthesizing this product was styrene / butyl acrylate / acrylic acid = 63/20/17, theoretical acid value 92, and molecular weight determined by GPC was 9000. The product was neutralized with potassium hydroxide to pH 8 (0.8 equivalent), and the resulting resin was used as surfactant 1-2, dissolved in water and used.

<Manufacture of resin fine particle dispersion 1>
[Production of Dispersion 1-1]
9.0 g of ethyl methacrylate, 1.0 g of hexadecyl methacrylate and 0.5 g of 2,2′-azobis- (2-methylbutyronitrile) were mixed in a reaction vessel and stirred for 1 hour at 100 rpm with a magnetic stirrer. The solid content was dissolved to obtain a mixed solution. This mixed solution was dropped into 70 g of an aqueous solution containing 0.3% of surfactant 1-1 and 0.3% of surfactant 1-2, and stirred at 300 rpm for 1 hour. Next, this solution was emulsified by irradiation with ultrasonic waves of 20 kHz for 1 hour with an ultrasonic irradiator (S-150D digital sonifier manufactured by Branson) to obtain dispersion 1-1.

[Production of Dispersion 1-2]
10 g of carbon black (trade name Printex 85 manufactured by Degussa) was added to 110 g of a mixed aqueous solution containing 1.3% of surfactant 1-1 and 1.3% of surfactant 1-2, and 600 rpm with a magnetic stirrer. For 2 hours. Thereafter, the solution was irradiated with an ultrasonic wave of 20 kHz for 5 hours with an ultrasonic irradiator and emulsified to obtain a dispersion 1-2.

[Production of Resin Fine Particle Dispersion 1]
20.0 g of Dispersion 1-1 and 80.0 g of Dispersion 1-2 were mixed in a reaction vessel and stirred with a magnetic stirrer at 600 rpm for 1 hour. After that, the ultrasonic wave was dispersed by irradiating 20 kHz ultrasonic waves for 6 minutes with an ultrasonic irradiator. Furthermore, it stirred at 600 rpm with the magnetic stirrer for 1 hour. Finally, a 20 kHz ultrasonic wave was irradiated for 6 minutes with an ultrasonic irradiator to obtain a dispersion.
This dispersion was kept at 70 ° C. under a nitrogen atmosphere, and a polymerization reaction was carried out for 8 hours. The obtained reaction liquid was filtered with a syringe filter (Minisart 17594K manufactured by Sartorius, pore size: 5.0 μm) to obtain resin fine particle dispersion 1.

<Manufacture of resin fine particle dispersion 2>
Reaction of 6.3 g of ethyl methacrylate, 0.7 g of hexadecyl methacrylate, 3 g of oil-based dye (trade name Orasol Blue GL, manufactured by Ciba Specialty Chemicals) and 0.5 g of 2,2′-azobis- (2-methylbutyronitrile) Mix in container. Next, the mixture was stirred with a magnetic stirrer at 100 revolutions per minute for 1 hour, and the solid content was dissolved to obtain a mixed solution. This mixed solution was dropped into 70 g of a mixed aqueous solution containing 0.3% of surfactant 1-1 and surfactant 1-2, and stirred at 300 rpm for 1 hour. Next, this solution was irradiated with ultrasonic waves of 20 kHz for 1 hour with an ultrasonic irradiator to obtain a dispersion. This dispersion was kept at 70 ° C. under a nitrogen atmosphere, and a polymerization reaction was carried out for 8 hours. The obtained reaction liquid was filtered with a syringe filter (Minisart 17594K manufactured by Sartorius, pore size: 5.0 μm) to obtain resin fine particle dispersion 2.

<Production of surfactant 2-1>
A reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 13.4 g (0.30 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 15.0 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 12.5 g was obtained.

  12.5 g (0.0080 mol) of the purified polyoxyethylene cetyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.93 g (0.0080 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours, and then cooled. Subsequently, the solid in the reaction vessel was taken out on a filter paper and washed with cold ion exchange water to obtain 11.7 g of purified sodium polyoxyethylene cetyl ether carboxylate (surfactant 2-1).

<Manufacture of resin fine particle dispersion 3>
The resin fine particle dispersion 3 was obtained in the same manner as in the production of the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to 2-1.

<Production of surfactant 3-1>
A reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 66.3 g (1.50 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 65.2 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 59.4 g was obtained.

  Purified polyoxyethylene cetyl ether 59.4 g (0.0087 mol) and sodium hydroxide 0.1 g were put in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 1.01 g (0.0087 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours, and then cooled. Next, the solid in the reaction vessel was taken out on a filter paper and washed with cold ion exchange water to obtain 52.9 g of purified sodium polyoxyethylene cetyl ether carboxylate (surfactant 3-1).

<Manufacture of resin fine particle dispersion 4>
The resin fine particle dispersion 4 was obtained in the same manner as the production of the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to 3-1.

<Manufacture of resin fine particle dispersion 5>
9.0 g of ethyl methacrylate, 1.0 g of hexadecyl methacrylate and 0.5 g of 2,2′-azobis- (2-methylbutyronitrile) were mixed in a reaction vessel and stirred for 1 hour at 100 rpm with a magnetic stirrer. The solid content was dissolved to obtain a mixed solution. This mixed solution was dropped into 70 g of a mixed aqueous solution containing 0.3% of surfactant 1-1 and 0.3% of surfactant 1-2, and stirred at 300 rpm for 1 hour. Next, this solution was irradiated with ultrasonic waves of 20 kHz for 1 hour with an ultrasonic irradiator to obtain a dispersion. This dispersion was kept at 70 ° C. under a nitrogen atmosphere, and a polymerization reaction was carried out for 8 hours. The obtained reaction liquid was filtered with a syringe filter (Minisart 17594K manufactured by Sartorius, pore size: 5.0 μm) to obtain resin fine particle dispersion 5.

<Production of surfactant 4-1>
A reaction vessel was charged with 1.30 g (0.01 mol) of octyl alcohol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 26.5 g of crude polyoxyethylene octyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred at 70 ° C. for 2 hours under reduced pressure, then filtered, and purified polyoxyethylene octyl ether 21.5 g was obtained.

21.5 g (0.0078 mol) of the purified polyoxyethylene octyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.90 g (0.0078 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours, and then cooled. Next, the solid matter in the reaction vessel was taken out on a filter paper. This was washed with cold ion-exchanged water, and purified polyoxyethylene octyl ether represented by the structural formula of C ₈ H ₁₇ O (CH ₂ CH ₂ O) _n —CH ₂ COONa (n is an integer of 1 or more). 18.7 g of sodium carboxylate (surfactant 4-1) was obtained.

<Manufacture of resin fine particle dispersion 6>
A resin fine particle dispersion 6 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 4-1, in the production of the resin fine particle dispersion 2.

<Production of surfactant 5-1>
18.8 g (0.010 mol) of polyoxyethylene octylphenyl ether (trade name Triton X-405, manufactured by Sigma Aldridge) and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 1.16 g (0.010 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours. After cooling, the solid in the reaction vessel was taken out on a filter paper. This is washed with cold ion-exchanged water, and is represented by the structural formula C ₈ H ₁₇ —C ₆ H ₄ —O— (CH ₂ CH ₂ O) _n —CH ₂ COONa (n is an integer of 1 or more). Purified sodium polyoxyethylene octylphenyl ether carboxylate (surfactant 5-1) 15.1 g was obtained.

<Manufacture of resin fine particle dispersion 7>
In the production of the resin fine particle dispersion 2, a resin fine particle dispersion 7 was obtained in the same manner as in the production of the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 5-1.

<Production of surfactant 6-1>
2.42 g (0.01 mol) of cetyl alcohol was placed in a reaction vessel, and a small amount of ion-exchanged water was added and mixed so that the water content in the raw material was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Subsequently, 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours while stirring at a pressure of 0.4 MPa and a temperature of 35 ° C., and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 21.1 g was obtained.

21.1 g (0.0073 mol) of purified polyoxyethylene cetyl ether was dissolved in 60 g of methylene chloride. Further, 0.73 g (0.0073 mol) of succinic anhydride and 0.58 g (0.0073 mol) of pyridine were added and reacted at room temperature with stirring for 15 hours. Then, extraction was performed twice with 1N hydrochloric acid aqueous solution. The resulting organic phase was further extracted twice with 5% aqueous potassium carbonate solution. Subsequently, the obtained organic phase was extracted twice with a saturated aqueous sodium chloride solution. About the obtained organic phase, the solvent was distilled off with an evaporator. This was dried under reduced pressure at 40 ° C. and 0.05 MPa, and represented by the structural formula of C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) _n —CO—CH ₂ CH ₂ COONa (n is an integer of 1 or more). 17.3 g of purified polyoxyethylene cetyl ether sodium succinate (surfactant 6-1) was obtained.

<Manufacture of resin fine particle dispersion 8>
A resin fine particle dispersion 8 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 6-1 in the production of the resin fine particle dispersion 2.

<Production of surfactant 7-1>
The reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol and 0.03 g of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene cetyl ether. Next, the pressure was reduced while maintaining the reaction vessel at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 21.1 g was obtained.

1.12 g (0.0073 mol) of phosphorus oxychloride was added to 21.1 g (0.0073 mol) of purified polyoxyethylene cetyl ether, and reacted while removing hydrogen chloride under reduced pressure. After completion of the reaction, the reaction mixture is cooled with cold water, purified, and purified polyoxyethylene cetyl ether phosphate represented by the structural formula of C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) _n —PO (OH) (ONa). 14.4 g of sodium ester (surfactant 7-1) was obtained.

<Manufacture of resin fine particle dispersion 9>
A resin fine particle dispersion 9 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 7-1 in the production of the resin fine particle dispersion 2.

<Manufacture of resin fine particle dispersion 10>
The resin fine particle dispersion 1 was produced in the same manner as the resin fine particle dispersion 1 except that the amount of the dispersion 1-1 was changed to 5.0 g and the amount of the dispersion 1-2 was changed to 95.0 g. Resin fine particle dispersion 10 was obtained.

<Manufacture of resin fine particle dispersion 11>
The resin fine particle dispersion 1 was produced in the same manner as the resin fine particle dispersion 1 except that the amount of the dispersion 1-1 was changed to 67.0 g and the amount of the dispersion 1-2 was changed to 33.0 g. Resin fine particle dispersion 11 was obtained.

<Surfactant 2-2>
MEK 50 g as a solvent, styrene 59 g, butyl acrylate 30 g and acrylic acid 10 g as a monomer were prepared in a 300 ml flask. After raising the temperature to 75 ° C. with stirring under a nitrogen stream, 1 g of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator to initiate polymerization, and the reaction was further continued for 7 hours. . After the reaction, the flask was cooled and diluted with 100 ml of MEK. As a result of charging this reaction liquid into hexane, a white product was obtained. The monomer ratio at the time of synthesizing this product was styrene / butyl acrylate / acrylic acid = 60/25/15, the theoretical acid value was 80, and the molecular weight determined by GPC was 12000. This product was neutralized with potassium hydroxide to pH 8 (0.8 equivalent), and the resulting resin was used as surfactant 2-2, dissolved in water and used.

<Manufacture of resin fine particle dispersion 12>
The resin fine particle dispersion 12 was obtained in the same manner as the resin fine particle dispersion 2 except that the surfactant 1-2 was changed to the surfactant 2-2 in the production of the resin fine particle dispersion 2.

<Surfactant 3-2>
MEK 50 g as a solvent, styrene 34 g, butyl acrylate 28 g and acrylic acid 39 g as a monomer were prepared in a 300 ml flask. After raising the temperature to 75 ° C. with stirring under a nitrogen stream, 1 g of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator to initiate polymerization, and the reaction was further continued for 7 hours. . After the reaction, the flask was cooled and diluted with 100 ml of MEK. As a result of charging this reaction liquid into hexane, a white product was obtained. The monomer ratio at the time of synthesizing the product was styrene / butyl acrylate / acrylic acid = 30/20/50, the theoretical acid value 302, and the molecular weight determined by GPC was 7000. This product was neutralized with potassium hydroxide to pH 8 (0.8 equivalent), and the resulting resin was used as surfactant 3-2, dissolved in water and used.

<Manufacture of resin fine particle dispersion 13>
A resin fine particle dispersion 13 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-2 was changed to the surfactant 3-2 in the production of the resin fine particle dispersion 2.

<Manufacture of resin fine particle dispersion 14>
In the production of the resin fine particle dispersion 1, it was produced in the same manner as the resin fine particle dispersion 1 except that the amount of the dispersion 1-1 was changed to 3.0 g and the amount of the dispersion 1-2 was changed to 97.0 g. A resin fine particle dispersion 14 was obtained.

<Manufacture of resin fine particle dispersion 15>
In the production of the resin fine particle dispersion 2, as the mixed aqueous solution containing the surfactant, 70 g of the mixed aqueous solution containing 0.51% of the surfactant 1-1 and 0.09% of the surfactant 1-2 was used. Was produced in the same manner as the resin fine particle dispersion 2, and a resin fine particle dispersion 15 was obtained.

<Manufacture of resin fine particle dispersion 16>
In the production of the resin fine particle dispersion 2, as the mixed aqueous solution containing the surfactant, 70 g of the mixed aqueous solution containing 0.18% of the surfactant 1-1 and 0.42% of the surfactant 1-2 was used. Was produced in the same manner as the resin fine particle dispersion 2, and a resin fine particle dispersion 16 was obtained.

<Manufacture of resin fine particle dispersion 17>
In the production of the resin fine particle dispersion 2, as the mixed aqueous solution containing the surfactant, 70 g of the mixed aqueous solution containing 0.06% of the surfactant 1-1 and 0.54% of the surfactant 1-2 was used. Was produced in the same manner as the resin fine particle dispersion 2, and a resin fine particle dispersion 17 was obtained.

<Manufacture of resin fine particle dispersion 18>
In the production of the resin fine particle dispersion 2, as the mixed aqueous solution containing the surfactant, 70 g of the mixed aqueous solution containing 0.15% of the surfactant 1-1 and 0.45% of the surfactant 1-2 was used. Was produced in the same manner as the resin fine particle dispersion 2, and a resin fine particle dispersion 18 was obtained.

<Manufacture of surfactant 8-1>
A reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. 80 g of a silica-based adsorbent (Kyoward 500SH; manufactured by Kyowa Chemical Industry) was added to the residue in the reaction vessel, and the mixture was stirred at 70 ° C. for 2 hours under reduced pressure. Next, filtration is performed, and purified polyoxyethylene cetyl ether (surfactant 8-1) represented by the structural formula of C ₁₆ H ₃₃ O (CH ₂ CH ₂ O) _n H (n is an integer of 1 or more) 21. 1 g was obtained.

<Manufacture of resin fine particle dispersion 21>
In the production of the resin fine particle dispersion 2, it was produced in the same manner as the resin fine particle dispersion 2 except that 70 g of an aqueous solution containing only 0.6% of the surfactant 8-1 was used as the mixed aqueous solution containing the surfactant. Resin fine particle dispersion 21 was obtained.

<Manufacture of resin fine particle dispersion 22>
In the production of the resin fine particle dispersion 2, it was produced in the same manner as the resin fine particle dispersion 2, except that 70 g of an aqueous solution containing only 0.6% of the surfactant 1-2 was used as the mixed aqueous solution containing the surfactant. Resin fine particle dispersion 22 was obtained.

<Production of surfactant 9-1>
24.2 g (0.10 mol) of cetyl alcohol was placed in a reaction vessel, and a small amount of ion-exchanged water was added and mixed so that the amount of water in the raw material was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 4.6 g (0.10 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 15.0 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 12.5 g was obtained.

  12.5 g (0.0080 mol) of the purified polyoxyethylene cetyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.93 g (0.0080 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours, and then cooled. Next, the solid matter in the reaction vessel was taken out on a filter paper and washed with cold ion exchange water to obtain 11.7 g of purified sodium polyoxyethylene cetyl ether carboxylate (surfactant 9-1).

<Manufacture of resin fine particle dispersion 23>
A resin fine particle dispersion 23 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 9-1 in the production of the resin fine particle dispersion 2.

<Surfactant 10-1>
A reaction vessel was charged with 1.02 g (0.01 mol) of hexyl alcohol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene hexyl ether 24 .8 g was obtained.

21.8 g (0.008 mol) of the purified polyoxyethylene hexyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.93 g (0.008 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours. After cooling, the solid in the reaction vessel was taken out on a filter paper. This was washed with cold ion-exchanged water, and purified polyoxyethylene hexyl ether carboxyl represented by the structural formula of C ₆ H ₁₃ O (CH ₂ CH ₂ O) _n —CH ₂ COONa (n is an integer of 1 or more). 14.6 g of sodium acid (surfactant 10-1) was obtained.

<Manufacture of resin fine particle dispersion 24>
The resin fine particle dispersion 24 was obtained in the same manner as the resin fine particle dispersion 2 except that the surfactant 1-1 was changed to the surfactant 10-1 in the production of the resin fine particle dispersion 2.

<Surfactant 11-1>
A reaction vessel was charged with 2.99 g (0.01 mol) of 1-eicosanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 26.6 g (0.60 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 27.6 g of crude polyoxyethylene eicosyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., the volatilization loss was measured, and the reaction rate of ethylene oxide was determined. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene eicosyl ether 26.0 g was obtained.

23.4 g (0.008 mol) of the purified polyoxyethylene eicosyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.93 g (0.008 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours. After cooling, the solid in the reaction vessel was taken out on a filter paper. This was washed with cold ion-exchanged water, and purified polyoxyethylene eicoethylene represented by the structural formula of C ₂₀ H ₄₁ —O— (CH ₂ CH ₂ O) _n —CH ₂ COONa (n is an integer of 1 or more). 14.6 g of sodium silethercarboxylate (surfactant 11-1) was obtained.

<Manufacture of resin fine particle dispersion 25>
A resin fine particle dispersion 25 was obtained in the same manner as in the resin fine particle dispersion 2, except that the surfactant 1-1 was changed to the surfactant 11-1 in the production of the resin fine particle dispersion 2.

<Manufacture of surfactant 12-1>
A reaction vessel was charged with 2.42 g (0.01 mol) of cetyl alcohol (a reagent manufactured by Wako Pure Chemical Industries) and a small amount of ion-exchanged water so that the water content was 0.1% by mass. Next, after adding 20 g of toluene, 4 g of anhydrous stannic chloride was charged at a temperature of 25 ° C., and the space portion of the reaction vessel was replaced with nitrogen gas to make the gauge pressure 0.05 MPa. Next, while maintaining the pressure at 0.4 MPa and the temperature at 35 ° C., 88.67 g (2.00 mol) of ethylene oxide was injected over 8 hours with stirring, and the reaction was continued for 1 hour after the injection. Thereafter, the reaction product was cooled to 10 ° C. to obtain 80 g of crude polyoxyethylene cetyl ether. Next, the reaction vessel was depressurized while being kept at 60 ° C., and the volatilization loss was measured to determine the reaction rate of ethylene oxide. After adding 80 g of silica-based adsorbent (KYOWARD 500SH; manufactured by Kyowa Chemical Industry Co., Ltd.) to the residue in the reaction vessel, the mixture was stirred under reduced pressure at 70 ° C. for 2 hours, then filtered, and purified polyoxyethylene cetyl ether 75 g was obtained.

  72.2 g (0.008 mol) of the purified polyoxyethylene cetyl ether and 0.1 g of sodium hydroxide were placed in a reaction vessel and stirred at a temperature of 60 ° C. for 4 hours. Thereafter, 0.93 g (0.008 mol) of sodium chloroacetate was added and heated at 40 ° C. for 8 hours, and then cooled. Next, the solid in the reaction vessel was taken out on a filter paper and washed with cold ion exchange water to obtain 14.6 g of purified sodium polyoxyethylene cetyl ether carboxylate.

<Manufacture of resin fine particle dispersion 26>
A resin fine particle dispersion 26 was obtained in the same manner as in the resin fine particle dispersion 2 except that the surfactant 1-1 was changed to the surfactant 12-1 in the production of the resin fine particle dispersion 2.

<Production of surfactant 4-2>
MEK 50 g as a solvent, 28 g of styrene as a monomer, 63 g of butyl acrylate and 10 g of acrylic acid were prepared in a 300 ml flask. After raising the temperature to 75 ° C. with stirring under a nitrogen stream, 1 g of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator to initiate polymerization, and the reaction was further continued for 7 hours. . After the reaction, the flask was cooled and diluted with 100 ml of MEK. As a result of charging this reaction liquid into hexane, a white product was obtained. The monomer ratio at the time of synthesizing this product was styrene / butyl acrylate / acrylic acid = 30/55/15, theoretical acid value 75, and molecular weight determined by GPC was 8,000. This product was neutralized with potassium hydroxide to pH 8 (0.8 equivalent), and the resulting resin was used as surfactant 4-2, dissolved in water and used.

<Manufacture of resin fine particle dispersion 27>
A resin fine particle dispersion 27 was obtained in the same manner as in the resin fine particle dispersion 2 except that the surfactant 1-2 was changed to the surfactant 4-2 in the production of the resin fine particle dispersion 2.

<Production of surfactant 5-2>
MEK 50 g as a solvent, styrene 11 g, butyl acrylate 47 g and acrylic acid 42 g as a monomer were prepared in a 300 ml flask. After raising the temperature to 75 ° C. with stirring under a nitrogen stream, 1 g of 2,2′-azobis (2-methylbutyronitrile) was added as a polymerization initiator to initiate polymerization, and the reaction was further continued for 7 hours. . After the reaction, the flask was cooled and diluted with 100 ml of MEK. As a result of charging this reaction liquid into hexane, a white product was obtained. The monomer ratio at the time of synthesizing the product was styrene / butyl acrylate / acrylic acid = 10/35/55, the theoretical acid value 325, and the molecular weight determined by GPC was 10,000. This product was neutralized with potassium hydroxide to pH 8 (0.8 equivalent), and the resulting resin was used as surfactant 5-2, dissolved in water and used.

<Manufacture of resin fine particle dispersion 28>
A resin fine particle dispersion 28 was obtained in the same manner as in the resin fine particle dispersion 2 except that the surfactant 1-2 was changed to the surfactant 5-2 in the production of the resin fine particle dispersion 2.

<Average particle diameter of resin fine particle dispersion>
Next, a method for measuring the particle size of the resin particle dispersion will be described.
The average particle size of the resin fine particle dispersions 1 to 28 was measured using a particle size distribution analyzer (Nikkiso Microtrac UPA EX-150) to measure the value of D50, which is the volume average median diameter of the resin fine particles.

Next, an ink manufacturing method will be described.
<Manufacture of ink 1>
42.0 g of resin fine particle dispersion 1, 5 g of glycerin, 5 g of 2-pyrrolidone and 5 g of polyethylene glycol (average molecular weight 1,000) were mixed, and 43.0 g of water was further added so that the total amount became 100 g. The mixture was stirred with a magnetic stirrer at 100 rpm for 1 day, and then filtered with a syringe filter (Sartorius Mini-Salto 17594K pore size 5.0 μm) to obtain ink 1.

<Manufacture of inks 2-9, 12, 13, 15-18, 21-28>
80.5 g of resin fine particle dispersion 2, 5 g of glycerin, 5 g of 2-pyrrolidone and 5 g of polyethylene glycol (average molecular weight 1,000) were mixed, and 4.5 g of water was further added so that the total amount became 100 g. The mixture was stirred with a magnetic stirrer at 100 rpm for 1 day, and then filtered with a syringe filter (Minisart 17594K, pore size 5.0 μm, manufactured by Sartorius) to obtain ink 2.
Further, in place of the resin fine particle dispersion 2, the ink fine particles 3 to 9, 12, 13, 13, 18 to 28 were used in the same manner except that the resin fine particle dispersions 3 to 9, 12, 13, 15 to 18, 21 to 28 were used. 15-18, 21-28 were obtained.

<Manufacture of ink 10>
37.3 g of resin fine particle dispersion 10, 5 g of glycerin, 5 g of 2-pyrrolidone and 5 g of polyethylene glycol (average molecular weight 1,000) were mixed, and 47.7 g of water was further added so that the total amount became 100 g. The mixture was stirred with a magnetic stirrer at 100 rpm for 1 day, and then filtered with a syringe filter (Sartorius Mini-Salto 17594K pore size 5.0 μm) to obtain ink 10.

<Manufacture of ink 11>
85.0 g of resin fine particle dispersion 11, 5 g of glycerin, 5 g of 2-pyrrolidone and 5 g of polyethylene glycol (average molecular weight 1,000) were mixed to prepare a total amount of 100 g. The mixture was stirred with a magnetic stirrer at 100 rpm for 1 day, and then filtered with a syringe filter (Sartorius Mini-Salto 17594K pore size 5.0 μm) to obtain ink 11.

<Manufacture of ink 14>
35.0 g of resin fine particle dispersion 14, 5 g of glycerin, 5 g of 2-pyrrolidone and 5 g of polyethylene glycol (average molecular weight 1,000) were mixed, and 50.0 g of water was further added so that the total amount became 100 g. The mixture was stirred with a magnetic stirrer at 100 rpm for 1 day, and then filtered with a syringe filter (Sartorius Mini-Salto 17594K pore size 5.0 μm) to obtain ink 14.

[Example 1]
The ejection stability of the ink 1 and suppression of bleeding were evaluated by the following methods and criteria. The results are shown in Table 1.

<Discharge stability>
The above inks 1 to 18, 21 to 28 were continuously discharged for 1 hour using an ink jet printer (PIXUS MX7600, manufactured by Canon), and the average discharge speed was measured.
〔Evaluation criteria〕
AA 15 m / second or more A 12 m / second or more and less than 15 m / second B 10 m / second or more and less than 12 m / second C Less than 10 m / second

<Suppression of bleed>
A reaction liquid having the following composition was filled in a PGI-2Clear ink tank of an ink jet printer (PIXUS MX7600 manufactured by Canon Inc.), and the reaction liquid was applied to PPC paper (manufactured by Canon Inc.). Thereafter, using the inks 1 to 18 and 21 to 28 described above, the letters “Emaze” were printed at 5 points with a background color of 100% duty.
[Composition of reaction solution]
・ Calcium nitrate tetrahydrate 16g
・ Glycerol 20g
・ Acetylene glycol ethylene oxide adduct (trade name: acetylenol E100) 1 g
・ 63 g of deionized water
〔Evaluation criteria〕
AA: The bleeding cannot be visually recognized, and the characters “Denatsu” are printed neatly.
A: Bleeding is hardly conspicuous, and it is easy to read the word “Denatsu”.
B: Although the outline of the word “Denki” is broken, it can be read.
C: The whole character of “Denatsu” blurs and is difficult to interpret.

[Examples 2 to 18]
Instead of ink 1, each of inks 2 to 18 was used to evaluate the ejection stability of each ink and the suppression of bleeding. The results are shown in Table 1.

[Comparative Examples 1-8]
Instead of the ink 1, the ink 21 to 28 was used, respectively, and the ejection stability of each ink and the suppression of bleeding were evaluated. The results are shown in Table 1.

Claims (7)

In a dispersion containing an α, β-unsaturated hydrophobic compound, a compound represented by the following general formula (1), and a water-soluble resin having an acid value of 80 or more and 315 or less, the α, β-unsaturation is performed. A resin fine particle dispersion obtained by polymerizing a hydrophobic compound.
General formula (1)
^{_{R 1 -O- (CH 2 CH 2}} O) k - (CO) l - (R 2) m -X n
(In the formula, R ¹ represents an alkyl group or an aryl group having 8 to 18 carbon atoms, R ² represents an alkylene group having 1 to 5 carbon atoms, X represents an anionic group, k is An integer of 30 or more and 150 or less, l represents 0 or 1, m represents 0 or 1, and n represents an arbitrary integer of 1 or more.   2. The resin fine particle dispersion according to claim 1, wherein a mass ratio of the compound represented by the general formula (1) and the water-soluble resin is in a range of 30:70 or more and 85:15 or less. X in the general formula (1) _{is, -COOM, -SO 3 M, -PO} 3 HM, claim 1 or an anionic group selected from the group consisting of -PO ₃ M ₂ and -SO ₂ NH ₂ The resin fine particle dispersion according to 2.
(In the formula, M represents a hydrogen atom or an alkali metal).   An ink-jet ink comprising the resin fine particle dispersion according to any one of claims 1 to 3. In a dispersion containing an α, β-unsaturated hydrophobic compound, a compound represented by the following general formula (1), a water-soluble resin having an acid value of 80 or more and 315 or less, and a colorant, the α, A color material-containing resin fine particle dispersion obtained by polymerizing a β-unsaturated hydrophobic compound.
General formula (1)
^{_{R 1 -O- (CH 2 CH 2}} O) k - (CO) l - (R 2) m -X n
(In the formula, R ¹ represents an alkyl group or an aryl group having 8 to 18 carbon atoms, R ² represents an alkylene group having 1 to 5 carbon atoms, X represents an anionic group, k is An integer of 30 or more and 150 or less, l represents 0 or 1, m represents 0 or 1, and n represents an arbitrary integer of 1 or more.   In the colorant-encapsulating resin fine particle dispersion, the content of the colorant is 0.4 to 20 times by mass with respect to the polymer content of the α, β-unsaturated hydrophobic compound. The coloring material-containing resin fine particle dispersion according to claim 5.   An ink-jet ink comprising the color material-encapsulating resin fine particle dispersion according to claim 5.