JP2015189809A - Resin particulate dispersion, inkjet recording ink, inkjet recording method, ink cartridge, and inkjet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin particulate dispersion which can be added to an inkjet recording ink as a binder composition, with excellent dispersion stability in an aqueous medium and high adhesion to coloring materials such as a pigment.SOLUTION: A resin particulate dispersion comprises an aqueous medium, and a resin particulate dispersed in the aqueous medium, the resin particulate being surface-modified with a benzimidazolinone derivative represented by the general formula (1) in the figure, where at least one of Zand Zis a polymerizable functional group.

Description

  The present invention relates to a resin fine particle dispersion, an ink jet recording method for ink jet recording, an ink cartridge, and an ink jet recording apparatus.

  In recent years, there is an increasing need for printing on coated printing paper with pigment inks excellent in weather resistance for inkjet recording. However, coated printing paper has lower ink permeability than plain paper or inkjet paper. For this reason, when printing with pigment ink on the coated printing paper, the pigment is deposited on the paper surface, and there is a problem that the scratch resistance of the recorded image is lowered.

  On the other hand, in order to improve the fixability of the pigment ink to the substrate and improve the scratch resistance of the image, a technique of adding a binder to the ink has been studied. Specifically, in order to record an image excellent in scratch resistance, an inkjet pigment ink to which latex is added as a binder has been proposed (Patent Documents 1 and 2). An ink for ink jet recording in which a binder is added as a microemulsion has been proposed (Patent Document 3). Furthermore, inks for inkjet recording in which a binder is added as a resin emulsion have also been proposed (Patent Documents 4 and 5).

JP 2001-106951 A JP 2003-171589 A JP-A-4-18462 JP-A-4-332774 JP-A-6-212106

  The resin fine particles for conventional binders added to the inks proposed in the above Patent Documents 1 to 5 are adjusted for the water resistance and dispersibility of the resin fine particles themselves by adjusting the type and composition ratio of the monomers constituting the resin. I tried to improve it. However, in Patent Documents 1 to 5, no consideration is given to the adsorptivity of these resin fine particles to a coloring material such as a pigment, and the recorded image is not sufficiently satisfactory in scratch resistance.

  Accordingly, the problem of the present invention is that it can be added to an ink for ink jet recording as a composition for a binder having excellent dispersion stability in an aqueous medium and having high adsorptivity to a coloring material such as a pigment. And providing a fine resin particle dispersion. Another object of the present invention is to provide an ink for ink jet recording using the resin fine particle dispersion, which is excellent in dispersion stability and capable of recording an image excellent in scratch resistance, and the ink jet recording. It is an object to provide an ink jet recording method, an ink cartridge, and an ink jet recording apparatus using an ink for use.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using resin fine particles whose surface is modified with a specific compound that can be adsorbed to a coloring material, and the present invention is completed. It came to.

That is, according to the present invention, the following resin fine particle dispersion is provided.
[1] A resin fine particle dispersion comprising: an aqueous medium; and resin fine particles surface-modified with a benzimidazolinone derivative represented by the following general formula (1) dispersed in the aqueous medium: body.

（前記一般式（１）中、Ｚ_l及びＺ_kは、それぞれ独立に、メチル基又は重合性官能基を示す。但し、Ｚ_l及びＺ_kの少なくとも一方は重合性官能基である）

(In the general formula (1), Z ₁ and Z _k each independently represent a methyl group or a polymerizable functional group, provided that at least one of Z ₁ and Z _k is a polymerizable functional group).

  [2] The resin fine particle dispersion according to [1], wherein the benzimidazolinone derivative is represented by the following formula (1-1).

  [3] Structural unit A derived from at least one of the monomer (A-1) represented by the following general formula (2) and the monomer (A-2) represented by the following general formula (3): And [1] or [2], wherein the raw material fine particles comprising a copolymer having a structural unit B derived from the monomer (B-1) represented by the following general formula (4) is surface-modified The resin fine particle dispersion described in 1.

^{_{CH 2 = CR 1 -COO- (CH}} 2 -CH 2 -O) m -R 2 ··· (2)
(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroaromatic hydrocarbon. And m represents an integer of 0 to 2)

^{_{CH 2 = CR 3 -Ar-R}} 4 ··· (3)
(In the general formula (3), R ³ represents a hydrogen atom or a methyl group, Ar represents a phenylene group, R ⁴ represents a hydrogen atom, —R ⁵ , —OR ⁵ , or —COOR ⁵ . And R ⁵ represents an alkyl group having 1 to 18 carbon atoms)

^{_{CH 2 = CR 6 -X-COOH}} ··· (4)
(In the general formula (4), R ⁶ represents a hydrogen atom or a methyl group, and X represents a single bond or a linear alkylene group having 1 to 9 carbon atoms, provided that in the linear alkylene group, —CH ₂ — may be substituted with —O—, —COO—, or —OCO— under the condition that no —O—O— bond occurs.

[4] The structural unit A is a structural unit derived from at least one selected from the group consisting of styrene, n-butyl acrylate, methyl methacrylate, and vinyl toluene, and the structural unit B is acrylic acid. The resin fine particle dispersion according to [3], which is a structural unit derived from at least one selected from the group consisting of methacrylic acid, 10-undecylenic acid, and 2-methacryloyloxyethyl succinate.
[5] The resin fine particle dispersion according to any one of [1] to [4], wherein the resin fine particle content is 3 to 30% by mass.
[6] The resin fine particle dispersion according to any one of [1] to [5], wherein the aqueous medium is water.

Moreover, according to this invention, the ink for inkjet recording shown below is provided.
[7] An inkjet recording ink comprising the resin fine particle dispersion according to any one of [1] to [6], a coloring material, and a water-soluble organic solvent.

Furthermore, according to the present invention, the following inkjet recording method, ink cartridge, and inkjet recording apparatus are provided.
[8] An ink jet recording method including a step of applying to a recording medium ink that has been ejected by applying energy, wherein the ink is the ink for ink jet recording described in [7]. Inkjet recording method.
[9] The inkjet recording method according to [8], wherein the energy is thermal energy.
[10] An ink cartridge comprising an ink containing portion containing ink, wherein the ink is the ink for ink jet recording described in [7].
[11] An ink jet recording apparatus comprising an ink cartridge having an ink containing portion containing ink and a head portion for discharging the ink, wherein the ink is for ink jet recording according to [7]. An ink jet recording apparatus comprising ink.

  According to the present invention, a resin that has excellent dispersion stability in an aqueous medium and has high adsorptivity to a coloring material such as a pigment and can be added to an ink for ink jet recording as a composition for a binder. A fine particle dispersion can be provided. In addition, according to the present invention, an ink for ink jet recording using the resin fine particle dispersion, which is excellent in dispersion stability and capable of recording an image excellent in scratch resistance, and the ink for ink jet recording An ink jet recording method, an ink cartridge, and an ink jet recording apparatus can be provided.

It is a schematic diagram explaining the structure of an ink cartridge. It is a schematic diagram explaining the structure of an inkjet recording head. It is a perspective view of an inkjet recording device. It is the schematic of the recovery processing system of an inkjet recording device. It is a schematic sectional drawing which shows another structural example of an inkjet recording head.

<Resin fine particle dispersion>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The resin fine particle dispersion of the present invention contains an aqueous medium and resin fine particles surface-modified with a benzimidazolinone derivative represented by the following general formula (1) dispersed in the aqueous medium. The details will be described below.

(Benzimidazolinone derivatives)
The benzimidazolinone derivative used in the resin fine particle dispersion of the present invention is a compound represented by the following general formula (1). This benzimidazolinone derivative is a compound that can be adsorbed on the surface of raw material fine particles made of a resin (polymer) constituting the resin fine particles.

（前記一般式（１）中、Ｚ_l及びＺ_kは、それぞれ独立に、メチル基又は重合性官能基を示す。但し、Ｚ_l及びＺ_kの少なくとも一方は重合性官能基である）

(In the general formula (1), Z ₁ and Z _k each independently represent a methyl group or a polymerizable functional group, provided that at least one of Z ₁ and Z _k is a polymerizable functional group).

  Since the benzimidazolinone derivative has a C═O bond and a nitrogen atom (N) in its molecule, it can be hydrogen-bonded to a hydrophilic group contained in a color material such as a pigment. The benzimidazolinone derivative has a plurality of unsaturated bonds and a benzene ring in the molecule. For this reason, the molecule | numerator of a benzimidazolinone derivative has high planarity, and since the (pi)-(pi) interaction with a coloring material is increased, it shows the strong adsorptivity with respect to a coloring material. Therefore, by modifying the surface of the raw material fine particles made of a resin (polymer) with a benzimidazolinone derivative, it is possible to provide a resin fine particle dispersion containing resin fine particles having excellent adsorptivity to a coloring material.

  The benzimidazolinone derivative can be synthesized according to a conventionally known method. For example, it can be synthesized according to the following schemes (1) to (3).

The molecular structure of the synthesized benzimidazolinone derivative includes a nuclear magnetic resonance apparatus ( ¹ H-NMR, for example, trade name “ECA400” manufactured by JEOL Ltd.), an infrared spectrophotometer (IR), and gel permeation chromatography. (GPC) or the like can be used for identification.

  Specific examples of preferred benzimidazolinone derivatives used in the resin fine particle dispersion of the present invention are shown below. However, the benzimidazolinone derivative used in the resin fine particle dispersion of the present invention is not limited to the preferred examples shown below.

(Resin fine particles)
The resin fine particle dispersion of the present invention contains resin fine particles that are surface-modified with the above-described benzimidazolinone derivative and dispersed in an aqueous medium. The resin fine particles are obtained, for example, by surface-modifying raw material fine particles made of a copolymer having specific structural units A and B with the benzimidazolinone derivative.

[Structural unit A]
The structural unit A is a structural unit derived from at least one of the monomer (A-1) represented by the following general formula (2) and the monomer (A-2) represented by the following general formula (3). In addition, the monomer (A-1) represented by following General formula (2) is (meth) acrylic acid ester and its derivative (s), for example. Moreover, the monomer (A-2) represented by following General formula (3) is styrene and its derivative (s).

^{_{CH 2 = CR 1 -COO- (CH}} 2 -CH 2 -O) m -R 2 ··· (2)
(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroaromatic hydrocarbon. And m represents an integer of 0 to 2)

^{_{CH 2 = CR 3 -Ar-R}} 4 ··· (3)
(In the general formula (3), R ³ represents a hydrogen atom or a methyl group, Ar represents a phenylene group, R ⁴ represents a hydrogen atom, —R ⁵ , —OR ⁵ , or —COOR ⁵ . And R ⁵ represents an alkyl group having 1 to 18 carbon atoms)

In the general formula (2), specific examples of the aliphatic hydrocarbon group represented by R ² include an alkyl group having 1 to 18 carbon atoms and an alkenyl group having 2 to 18 carbon atoms. Of these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group, an isopropyl group, and an n-butyl group are more preferable. Specific examples of the alicyclic hydrocarbon group represented by R ² in the general formula (2) include a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and the like. Can do.

In the general formula (2), specific examples of the aromatic hydrocarbon group represented by R ² include an aromatic hydrocarbon group having 6 to 18 carbon atoms. Of these, a phenyl group is preferred. The “aromatic hydrocarbon group” includes a group in which a hydrogen atom on an aromatic ring is substituted with a hydrocarbon group. For example, a benzyl group, an alkylphenyl group, a biphenyl group and the like are preferable. In the general formula (2), specific examples of the heteroaromatic hydrocarbon group represented by R ² include a group in which the carbon atom constituting the aromatic ring of the aromatic hydrocarbon group is substituted with a nitrogen atom (for example, , Phenylpyridyl group) and the like.

  Specific examples of the monomer (A-1) include (meth) acrylic acid esters such as methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methyl acrylate, isopropyl acrylate, and n-butyl acrylate (m = 0); ethoxyalkyl (meth) acrylates such as 2-ethoxyethyl methacrylate and 2-ethoxyethyl acrylate (m = 1); 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (acrylic acid 2- ( (Methoxy) acrylic acid ethoxyethoxyalkyls such as 2-ethoxyethoxy) ethyl (m = 2); Of these, methyl methacrylate and n-butyl acrylate are preferable in terms of ejection stability of the ink for inkjet recording.

Specific examples of the monomer in which R ⁴ in the general formula (3) is a hydrogen atom include α-methylstyrene and styrene. Of these, styrene is preferable in terms of ejection stability of the ink for inkjet recording. In general formula (3), the alkyl group having 1 to 18 carbon atoms represented by R ⁵ includes a methyl group, an ethyl group, an n-butyl group, an n-dodecyl group, an n-hexadecyl group, and an n-octadecyl group. Etc. are preferred.

Specific examples of the monomer in which R ⁴ in the general formula (3) is a group represented by —R ⁵ include 1-methyl-4-vinylbenzene and 1-ethyl-4- (propen-2-yl) benzene. 1-butyl-4- (propen-2-yl) benzene, 1-dodecyl-4- (propen-2-yl) benzene and the like. Of these, 1-methyl-4-vinylbenzene (also known as 4-methylstyrene) is preferable in terms of ejection stability of ink for ink jet recording.

Specific examples of the monomer in which R ⁴ in the general formula (3) is a group represented by —OR ⁵ include 4-methoxy-vinylbenzene, 4-butoxy-vinylbenzene and the like. Specific examples of the monomer in which R ⁴ in the general formula (3) is a group represented by —COOR ⁵ include methyl-4-vinylbenzoate, butyl-4-vinylbenzoate, dodecyl-4-vinylbenzoate, Examples include hexadecyl-4-vinylbenzoate and octadecyl-4-vinylbenzoate.

[Structural unit B]
The structural unit B is a structural unit derived from the monomer (B-1) represented by the following general formula (4). The monomer (B-1) represented by the following general formula (4) is a monomer having a carboxy group at its terminal.

^{_{CH 2 = CR 6 -X-COOH}} ··· (4)
(In the general formula (4), R ⁶ represents a hydrogen atom or a methyl group, and X represents a single bond or a linear alkylene group having 1 to 9 carbon atoms, provided that in the linear alkylene group, —CH ₂ — may be substituted with —O—, —COO—, or —OCO— under the condition that no —O—O— bond occurs.

  Specific examples of the monomer (B-1) include (meth) acrylic acids such as methacrylic acid and methacrylic acid; 2-methacryloyloxyethyl succinate; 10-undecylenic acid and the like. Of these, acrylic acid having high hydrophilicity is preferable in terms of dispersion stability of the ink for inkjet recording.

  If the copolymer forming the raw material fine particles has only the structural unit A, the adhesion between the resin fine particles and the recording medium such as coated paper may be lowered. On the other hand, when the copolymer forming the raw material fine particles has only the structural unit B, the water solubility becomes too high due to the presence of a carboxy group at the terminal of the monomer (B-1), and resin fine particles are not formed. Or, even if resin fine particles are formed, the water resistance may decrease. For this reason, it is preferable that the copolymer forming the raw material fine particles has the structural unit A and the structural unit B. The structural unit A is a structural unit derived from at least one selected from the group consisting of styrene, n-butyl acrylate, methyl methacrylate, and vinyl toluene, and the structural unit B is acrylic acid, methacrylic acid. It is preferably a structural unit derived from at least one selected from the group consisting of 10-undecylenic acid and 2-methacryloyloxyethyl succinate.

  The weight average molecular weight of the copolymer forming the raw material fine particles is preferably 1,000 to 600,000. When the weight average molecular weight is 1,000 or more, the scratch resistance of the image can be further improved when the film is formed. Moreover, since the solubility to a solvent can be improved as a weight average molecular weight is 600,000 or less, a uniform film can be formed. In addition, the weight average molecular weight of a copolymer can be measured by various chromatography including a gel permeation chromatography (GPC), a static light scattering (Static Light Scattering: SLS) etc., for example.

(Method for producing resin fine particle dispersion)
For example, when a dry powder of resin fine particles is added to an aqueous medium, the dispersion of resin fine particles may be insufficient. For this reason, the resin fine particle dispersion of the present invention is preferably obtained in a state where the resin fine particles are dispersed in an aqueous medium by emulsion polymerization of the monomer. Although the method for producing the resin fine particle dispersion of the present invention is not particularly limited, it can be produced, for example, according to the following method.

A predetermined amount of a monomer and a benzimidazolinone derivative are placed in a 300 mL four-necked flask equipped with a stirring seal, a stirring rod, a reflux condenser, a septum rubber, and a nitrogen introduction tube, and nitrogen is used for 1 hour. Add 100 g of ion-exchanged water while stirring at 300 rpm. Polymerization is initiated by heating to 80 ° C. in a thermostatic bath and injecting an initiator dissolved in an appropriate amount of ion exchange water into the flask with a syringe. By polymerizing while monitoring the polymerization state by GPC and ¹ H-NMR, a resin fine particle dispersion containing the desired resin fine particles can be obtained.

  When producing resin fine particles that cannot be self-dispersed, a surfactant is usually used during polymerization. The surfactant promotes emulsification or particle formation of the copolymer and suppresses aggregation and sedimentation of the resin particles. On the other hand, in the method for producing the resin fine particle dispersion, a normal surfactant is not used, but a resin fine particle dispersion in a good dispersion state can be obtained. This is because the benzimidazolinone derivative is adsorbed on the surface of the raw material fine particles formed by polymerization by adding the benzimidazolinone derivative in the polymerization system, and the benzimidazolinone derivative is interfaced at the interface between the raw material fine particles and the aqueous medium. It is presumed that this is because the same role as the activator was played.

  Since the benzimidazolinone derivative has a highly polar C═O bond and a nitrogen atom (N) and a less polar benzene ring portion in its molecule, it has a slight surface activity. For this reason, when ion-exchanged water is added to a mixture of a predetermined monomer and a benzimidazolinone derivative, the benzimidazolinone derivative functions as an emulsifier having surface activity and exists on the surface of emulsion particles formed by the monomer. Thereafter, by adding an initiator into the polymerization system, the radical generated from the initiator reacts with the monomer to initiate the polymerization reaction. Raw material fine particles are formed with the growth of the reaction product (copolymer), and a benzimidazolinone derivative is present at the interface between the formed raw material fine particles and the aqueous medium.

  After the polymerization reaction, the unreacted monomer may be removed by purification. Examples of the purification means include dialysis, activated carbon adsorption, ultrafiltration, and centrifugation. Thereafter, a resin fine particle dispersion can be obtained through steps such as pH adjustment, solvent replacement, and concentration adjustment.

  The volume cumulative median diameter of the resin fine particles in the resin fine particle dispersion is preferably 80 nm or more and 900 nm or less. Although depending on the glass transition temperature of the resin, in the thermal ink jet recording method in which the image is recorded by applying the ink that has been ejected by applying thermal energy to the recording medium, the volume cumulative median diameter of the resin fine particles is 80 nm. If it is less than the range, the discharge tends to be unstable. On the other hand, when the volume cumulative median diameter of the resin fine particles exceeds 900 nm, the surface of the image recorded on the recording medium tends to be uneven, and the image scratch resistance tends to decrease.

  The resin fine particle content in the resin fine particle dispersion is preferably 3 to 30% by mass. When the content of the resin fine particles is 3% by mass or more, an ink for inkjet recording capable of imparting a sufficient color density can be prepared. Further, when the content of the resin fine particles is 30% by mass or less, an ink for inkjet recording having excellent dispersion stability can be obtained.

  The acid value of the resin (copolymer) constituting the raw material fine particles is preferably 0 mgKOH / g or more and 304 mgKOH / g or less. The acid value of the resin is represented by the amount (mg) of KOH required to neutralize 1 g of resin. When the acid value of the resin is more than 304 mgKOH / g, the viscosity of the resin fine particle dispersion becomes high and the discharge tends to be unstable. The acid value of the resin can be calculated from the composition ratio of each monomer constituting the resin, but can also be measured by potentiometric titration using a trade name “Titrino” (manufactured by Metrohm) or the like.

  In addition, when resin (copolymer) which comprises raw material fine particles contains the structural unit B, the electronic repulsion between copolymers is enlarged by neutralizing the carboxy group in the structural unit B with a base. Further, the dispersion stability of the resin fine particles can be further improved. The base that neutralizes the carboxy group is preferably a monovalent alkyl metal hydroxide, more preferably potassium hydroxide. Further, the pH of the resin fine particle dispersion is preferably 8.0 to 10.0, and more preferably 8.4 to 9.8. When the pH of the resin fine particle dispersion is within the above range, the long-term storage stability of the obtained ink jet recording ink can be improved, and a decrease in ink dischargeability after long-term storage can be suppressed.

(Aqueous medium)
The resin fine particle dispersion of the present invention contains an aqueous medium that is a medium in which resin fine particles are dispersed. As the aqueous medium, for example, water or a mixed solvent of water and a water-soluble organic solvent can be used.

  It is preferable to use ion exchange water as water. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propanol and isopropanol; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether; ketones such as acetone and methyl ethyl ketone; And ethers such as tetrahydrofuran;

  The mixing ratio of the mixed solvent of water and the water-soluble organic solvent is not particularly limited. However, it is preferable to use only water as the aqueous solvent.

<Ink for inkjet recording>
The ink for inkjet recording of the present invention (hereinafter also simply referred to as “ink”) contains the above-described resin fine particle dispersion, a color material, and a water-soluble organic solvent. That is, the ink of the present invention can be produced by adding a colorant, various solvents such as a water-soluble organic solvent, and additives as necessary to the above-described resin fine particle dispersion.

  The content of the resin fine particles in the ink is preferably 0.5 to 5% by mass. When the content of the resin fine particles is 0.5% by mass or more, an image having excellent scratch resistance can be recorded. Further, when the content of the resin fine particles is 5% by mass or less, a low-viscosity ink can be obtained.

  The content of the color material in the ink is preferably 1 to 5% by mass. When the content of the color material is 1% by mass or more, an image having excellent color developability can be recorded. Further, when the content of the color material is 5% by mass or less, a low-viscosity ink can be obtained.

  The content ratio between the resin fine particles and the color material is preferably a solid mass ratio, and the resin fine particles: color material = 1: 2 to 2: 1. When the content of the color material is ½ or more of the content of the resin fine particles, the ink can be excellent in ejection stability. Further, when the content of the color material is not more than twice the content of the resin fine particles, the ink can be excellent in storage stability and image fixability.

  A benzimidazolinone derivative is a compound that is easily adsorbed to a coloring material. Therefore, it is preferable that the benzimidazolinone derivative is present on the surface of the resin fine particles because the resin fine particles easily adsorb the coloring material. However, dispersibility is maintained even in a mixture of resin fine particles surface-modified with a benzimidazolinone derivative and a coloring material in the liquid. This is presumably due to the following reasons.

  A benzimidazolinone derivative has a —NH— group in its molecule, but is considered to be hydrated in water. For this reason, even if a color material is present in the vicinity of the resin fine particles, the adsorption of the benzimidazolinone derivative and the color material is inhibited by water molecules, so that the resin surface-modified with the benzimidazolinone derivative in aqueous ink. The dispersion stability of the fine particles is maintained. The resin fine particles and the colorant that are surface-modified with a benzimidazolinone derivative may exist in the same ink, or may exist in different inks. After the ink has landed on the recording medium, the concentration of the resin fine particles and the color material on the recording medium increases as the recording medium absorbs the solvent or the solvent scatters in the atmosphere. At this time, when the water molecules that have prevented the adsorption of the benzimidazolinone derivative and the coloring material are reduced, the distance between the benzimidazolinone derivative and the coloring material is shortened, and the adsorption between the resin fine particles and the coloring material occurs. Conceivable.

(Color material)
As the color material, for example, a pigment such as carbon black, a yellow / magenta / cyan pigment, an oil-soluble dye, or the like can be used. The benzimidazolinone derivative used in the resin fine particle dispersion of the present invention exhibits excellent adsorption performance for any of these coloring materials. However, when producing resin fine particles using a benzimidazolinone derivative, confirm the adsorptivity of the benzimidazolinone derivative to the target colorant and select a benzimidazolinone derivative having a more preferable structure. It is effective to use.

  Specific examples of the pigment and oil-soluble dye black type, the following trade names, Raven760Ultra, Raven1060Ultra, Raven1080, Raven1100Ultra, Raven1170, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500Ultra, Raven3500, Raven5250, Raven5750, Raven7000, Raven5000ULTRAII Raven 1190 ULTRA II (above Colombian Carbon)

  BlackPearlsL, MOGUL-L, Regal400R, Regal660R, Regal330R, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1300, Monarch1400 (above, manufactured by Cabot);

  ColorBlackFW1, ColorBlackFW2, ColorBlackFW200, ColorBlack18, ColorBlackS160, ColorBlackS170, SpecialBlack4, SpecialBlack4A, SpecialBlack6, SpecialBlack550, Printex35, Printex45, Printex55, Printex85, Printex95, PrintexU, Printex140U, PrintexV, Printex140V (manufactured by Degussa);

  No. 25, no. 33, no. 40, no. 45, no. 47, no. 52, no. 900, no. 970, no. 2200B, no. 2300, no. Other than 2400B, MCF-88, MA600, MA77, MA8, MA100, MA230, MA220 (above, manufactured by Mitsubishi Chemical Corporation);

  C. I. Solvent black 3, 5, 7, 8, 14, 17, 19, 20, 22, 24, 26, 27, 28, 29, 43, 45 etc. can be mentioned.

  Examples of yellow pigments and oil-soluble dyes include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. More specifically, C.I. I. Pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, C.I. I. Solvent Yellow 1, 2, 3, 13, 14, 19, 21, 22, 29, 36, 37, 38, 39, 40, 42, 43, 44, 45, 47, 62, 63, 71, 74, 76, 79, 81, 82, 83: 1, 85, 86, 88, 151 and the like.

  Examples of magenta pigments and oil-soluble dyes include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolinone compounds, thioindigo compounds, and perylene compounds. Can do. More specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Solvent Red 8, 27, 35, 36, 37, 38, 39, 40, 49, 58, 60, 65, 69, 81, 83: 1, 86, 89, 91, 92, 97, 99, 100, 109, 118, 119, 122, 127, 218 and the like.

  Examples of cyan pigments and oil-soluble dyes include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. More specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, C.I. I. Solvent blue 14, 24, 25, 26, 34, 37, 38, 39, 42, 43, 44, 45, 48, 52, 53, 55, 59, 67, 70 can be mentioned.

(Water-soluble organic solvent)
The ink of the present invention contains a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol; ethylene glycol, diethylene glycol, tri Ethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, thiodiglycol, 1,4-cyclohexanediol, etc. Diols; triols such as 1,2,4-butanetriol, 1,2,6-hexanetriol, 1,2,5-pentanetriol; trimethylolpropane, trimethylol Hindered alcohols such as tan, neopentyl glycol, pentaerythritol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoallyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Glycol ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether; glycerin, dimethyl sulfoxide, glycerin monoallyl ether, polyethylene glycol, N-methyl-2 -Pyrrolide , 2-pyrrolidone, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, sulfolane, β-dihydroxyethylurea, urea, acetonylacetone, dimethylformamide, dimethylacetamide, acetone, diacetone alcohol, etc. Can do.

(Various additives)
Various additives may be added to the resin fine particle dispersion and the ink of the present invention as needed as long as the effects of the present invention are not impaired. Examples of the various additives include conventionally known surfactants, pH adjusters, antioxidants, and antifungal agents that are blended in the ink composition and the like.

<Inkjet recording method, ink cartridge, inkjet recording apparatus>
The ink jet recording method of the present invention includes a step of applying to a recording medium ink that has been ejected by applying energy. The ink-jet recording ink described above is used as the ink. As energy, thermal energy or mechanical energy can be used. Among these, it is preferable to use thermal energy.

  The type of recording medium used in the inkjet recording method of the present invention is not particularly limited. As the recording medium, so-called inkjet exclusive paper, postcards, business card paper, label paper, cardboard paper, inkjet film, various copy papers, and the like are preferable. A recording medium having a coating layer can also be used. As a recording medium having a coating layer, a recording medium containing at least one of a hydrophilic polymer and an inorganic porous material and having a coating layer for receiving ink on at least one surface is preferable.

  Examples of the ink jet recording apparatus that records an image using the ink of the present invention include a general household printer mainly using A4 size paper, a printer for printing business cards and cards, and a large business printer. Can do. Hereinafter, a suitable inkjet recording apparatus will be described with an example.

(Inkjet recording device using thermal energy)
FIG. 1 is a schematic diagram illustrating the configuration of the ink cartridge. The ink cartridge 100 contains ink that is supplied to the head via the ink supply tube 104. A plug 102 made of chlorinated butyl rubber is provided at the tip of the ink bag 101 containing the supply ink. By inserting the needle 103 into the stopper 102, the ink in the ink bag 101 can be supplied to the recording head (303 to 306). An ink absorber that receives waste ink may be provided in the ink cartridge. The ink jet recording apparatus used in the present invention is not limited to the one in which the recording head and the ink cartridge are separated as described above, and an apparatus in which they are integrated is also preferably used.

  FIG. 2 is a schematic diagram illustrating the structure of the ink jet recording head. Each nozzle 202 is provided with a corresponding heating element (heater 204), and is heated by applying a predetermined driving pulse from the recording head driving circuit to the heater 204 to generate bubbles. Ink droplets are discharged from the discharge port 202. The heater 204 is formed on the silicon substrate 206 by the same method as in the semiconductor manufacturing process. Reference numeral 203 denotes a nozzle partition that constitutes each nozzle 202, reference numeral 205 denotes a common liquid chamber for supplying ink to each nozzle 202, and reference numeral 207 denotes a top plate.

  FIG. 3 is a perspective view of the ink jet recording apparatus. The recording paper 302 of the recording apparatus 300 is supplied from, for example, a roll supply unit 301 and is continuously conveyed by a conveyance unit provided in the main body of the recording apparatus 300. The transport unit includes a transport motor 312 and a transport belt 313. In recording, when the image cut-out position of the recording material passes under the black recording head 303, the black ink starts to be ejected from the recording head. Similarly, cyan 304, magenta 305, and yellow 306 are sequentially printed for each color. A color image is formed by selectively ejecting ink.

  In addition, the recording apparatus 300 includes a cap mechanism 311 that caps each recording head during standby, ink cartridges 307 to 310 for supplying ink to each recording head 303 to 306, and ink supply and recovery operations. A pump unit (not shown), a control board (not shown) for controlling the entire recording apparatus, and the like are configured.

  FIG. 4 is a schematic diagram of a recovery processing system of the ink jet recording apparatus. When the recording heads 303 to 306 are lowered, a predetermined recovery operation can be executed when the ink discharge port formation surface comes close to the cap 400 formed of chlorinated butyl rubber in the cap mechanism 311.

  The ink regenerating circuit unit in the recovery processing system connects the ink cartridge 100 in which the replenished ink is stored and accommodated in the polyethylene bag; the sub tank 401 connected through the suction pump 403 and the like; the cap 400 and the sub tank 401 are connected to each other. A suction pump 403 disposed in an ink supply path 409 formed of vinyl chloride and collecting the ink from the cap mechanism 311 in the sub tank 401; a filter 405 for removing dust and the like in the ink recovered from the cap; an ink supply path 408 A pressure pump 402 for supplying ink to a common liquid chamber of the recording heads 303 to 306; an ink supply path 407 for supplying ink returned from the recording head to the sub tank 401; and valves 404a to 404d as main elements. It is configured.

  When cleaning the recording heads 303 to 306, the recovery valve 404 b is closed and the pressure pump 402 is operated to pressurize and supply ink from the sub tank 401 to the recording head and forcibly discharge from the nozzle 406. Thereby, bubbles, ink, dust and the like in the nozzles of the recording head are discharged. The suction pump 403 collects the ink discharged from the recording head into the cap mechanism 311 in the sub tank 401.

(Inkjet recording device using mechanical energy)
Next, a preferred example of an ink jet recording apparatus using mechanical energy will be described. As an ink jet recording apparatus using mechanical energy, for example, a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material arranged opposite to the nozzles, and a periphery of the pressure generating element And a recording apparatus including an on-demand ink jet recording head that displaces a pressure generating element by an applied voltage and discharges a small droplet of ink from a nozzle. FIG. 5 is a schematic cross-sectional view showing another configuration example of the ink jet recording head.

  The head includes an ink flow path 80 communicating with an ink chamber (not shown), an orifice plate 81 for ejecting ink droplets of a desired volume, a vibration plate 82 that directly applies pressure to ink, and the vibration plate 82. And a substrate 84 for indicating and fixing the orifice plate 81, the vibration plate 82, and the like.

  In FIG. 5, an ink flow path 80 is formed of a photosensitive resin or the like, an orifice plate 81 is formed with a discharge port 85 by drilling a metal such as stainless steel or nickel by electroforming or pressing, and the diaphragm 82 is The piezoelectric element 83 is formed of a dielectric material such as barium titanate or PZT. The piezoelectric element 83 is formed of a metal film such as stainless steel, nickel, or titanium and a highly elastic resin film. The recording head configured as described above applies a pulsed voltage to the piezoelectric element 83 to generate strain stress, and the energy deforms the vibration plate 82 bonded to the piezoelectric element 83, so that the inside of the ink flow path 80. An operation is performed so as to perform recording by pressurizing the ink vertically and ejecting ink droplets (not shown) from the ejection port 85 of the orifice plate 81.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited at all by the following Example, unless the summary is exceeded. In addition, what is described as “parts” and “%” with respect to the component amounts is based on mass unless otherwise specified.

The molecular structure of the synthesized benzimidazolinone derivative was identified using a nuclear magnetic resonance apparatus ( ¹ H-NMR, trade name “ECA400”, manufactured by JEOL Ltd., solvent: tetrahydrofuran-d8). The weight average molecular weight of the resin fine particles is measured using GPC (trade name “HLC8220” manufactured by Tosoh Corporation, column: TSK-GEL4000HXL, TSK-GEL3000HXL, TSK-GEL2000HXL, column oven temperature: 40.0 ° C.). did.

<Synthesis of Intermediate 1>
Into a 1 L four-necked flask equipped with a stirring seal, stirring rod, dropping funnel, septum rubber, nitrogen inlet tube, and thermometer, 15 parts (0.1 mol) of 5-amino-2-benzimidazolinone and 9% 138 parts (0.34 mol) of dilute hydrochloric acid was added and cooled to 5 ° C. or lower. 37 parts (0.1 mol) of an 18.7% aqueous sodium nitrite solution was added dropwise while cooling with ice to prepare a diazonium salt solution. On the other hand, 230 parts of ethanol and 126 parts (0.56 mol) of 36.5% sodium acetate aqueous solution were added to 12 parts (0.1 mol) of methyl acetoacetate and stirred, and the solution was cooled to 5 ° C. or lower. Prepared. The diazonium salt solution was slowly added dropwise to the prepared solution, and the mixture was stirred for 30 minutes under ice cooling and further for 1 hour at room temperature. Thereafter, the produced precipitate was collected by filtration, washed with water and dried to obtain an intermediate 1 (yield 97%).

<Synthesis of Intermediate 2>
In a 1 L four-necked flask equipped with a stirring seal, stirring rod, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 47 parts of ion-exchanged water and 20 parts of sodium hydroxide were added and stirred. After confirming that the sodium hydroxide was completely dissolved, 94 parts of methanol was added and stirred. 138 parts (0.5 mol) of Intermediate 1 was added and stirred at room temperature for 2 hours. Then, while distilling off methanol, the generated precipitate was collected by filtration, washed with water and dried to obtain Intermediate 2 (yield 98%).

<Synthesis of benzimidazolinone derivative 1>
Into a 1 L four-necked flask equipped with a stirring seal, stirring rod, dropping funnel, septum rubber, nitrogen inlet tube, and thermometer, 12.0 parts (0.04 mol) of Intermediate 2 obtained above and pyridine 170 were obtained. The intermediate 1 was dissolved in pyridine and cooled to 5 ° C. or lower. Then, 16.7 parts (0.16 mol) of methacryloyl chloride dissolved in 90 parts of pyridine was dropped and stirred for 1 hour. Thereafter, 200 parts of water was added to stop the reaction, separation by centrifugation and washing with water were performed to obtain a benzimidazolinone derivative 1 represented by the formula (1-1) (yield 70%).

<Synthesis of Intermediate 3>
Intermediate 2 was synthesized by the same method as “Synthesis of Intermediate 1” described above, except that methyl acetoacetate was changed to 13 parts (0.1 mol) of dimethyl malonate (yield 97%).

<Synthesis of Intermediate 4>
Intermediate 4 was synthesized (98% yield) by the same method as “Synthesis of Intermediate 2” described above, except that Intermediate 1 was changed to 146 parts (0.5 mol) of Intermediate 3.

<Synthesis of benzimidazolinone derivative 2>
Except that the intermediate 2 was changed to 9.9 parts (0.04 mol) of the intermediate 4 and the amount of methacryl chloride was changed to 33.4 parts (0.32 mol), the above-mentioned “benzimidazo” The benzimidazolinone derivative 2 represented by the formula (1-2) was synthesized by the same method as in “Synthesis of Rinone Derivative 1” (yield 50%).

<Synthesis of benzimidazolinone derivative 3>
Except that methacryl chloride was changed to 14.5 parts (0.16 mol) of acryloyl chloride, it was represented by the above s (1-3) in the same manner as in the above-mentioned “Synthesis of benzimidazolinone derivative 1”. Benzimidazolinone derivative 3 was synthesized (yield 70%).

<Synthesis of benzimidazolinone derivative 4>
It is represented by the above formula (1-4) by the same method as the above-mentioned “Synthesis of benzimidazolinone derivative 2> except that methacryl chloride is changed to 29.0 parts (0.32 mol) of acryloyl chloride. A benzimidazolinone derivative 4 was synthesized (yield 50%).

<Synthesis of benzimidazolinone derivative 5>
Benzimidazolinone derivative 5 was synthesized in the same manner as in the above-mentioned “Synthesis of Intermediate 1” except that methyl acetoacetate was changed to 10 parts (0.1 mol) of acetylacetone (yield 98%).

<Confirmation of surface activity of benzimidazolinone derivatives>
In a beaker, 0.2115 parts (0.6410 mmol) of benzimidazolinone derivative 1, 17.116 parts (1333.4758 mmol) of n-butyl acrylate, 8.6079 parts (82.6491 mmol) of styrene, 4. 3073 parts (59.7738 mmol) and 100 parts of ultrapure water were added and mixed by stirring to obtain a suspension. On the other hand, after placing 200 parts of ultrapure water in another beaker and installing an electric conductivity meter (trade name “ES-12”, manufactured by HORIBA) so that the tip of the ultrapure water is in contact with the liquid surface, the suspension is suspended while stirring The suspension was added dropwise. Simultaneously with the dropwise addition, a graph was prepared by plotting the value of the electric conductivity meter on the vertical axis and the concentration in the mixed solution of benzimidazolinone derivative 1 on the horizontal axis. As a result, the created graph had an inflection point, and the surface activity of the benzimidazolinone derivative 1 could be confirmed. The value on the horizontal axis (= CMC: Critical Micule Concentration (critical micelle concentration)) was 0.60%.

  The surface active ability was confirmed in the same manner as in the case of the benzimidazolinone derivative 1 except that the benzimidazolinone derivative 1 was changed to 0.2564 part (0.6410 mmol) of the benzimidazolinone derivative 2. As a result, the surface activity of benzimidazolinone derivative 2 could be confirmed. Further, the critical micelle concentration of benzimidazolinone derivative 2 was 0.40%.

  The surface activity was confirmed in the same manner as in the case of the benzimidazolinone derivative 1 except that the benzimidazolinone derivative 1 was changed to 0.2026 part (0.6410 mmol) of the benzimidazolinone derivative 3. As a result, the surface activity of benzimidazolinone derivative 3 could be confirmed. Further, the critical micelle concentration of benzimidazolinone derivative 3 was 0.59%.

  The surface activity was confirmed in the same manner as in the case of the benzimidazolinone derivative 1 except that the benzimidazolinone derivative 1 was changed to 0.2385 parts (0.6410 mmol) of the benzimidazolinone derivative 4. As a result, the surface activity of benzimidazolinone derivative 4 could be confirmed. Further, the critical micelle concentration of benzimidazolinone derivative 4 was 0.39%.

<Confirmation of reactivity of polymerizable functional group of benzimidazolinone derivative>
In a 300 mL four-necked flask equipped with a stirring seal, stirring bar, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 0.2115 parts (0.6410 mmol) of benzimidazolinone derivative 1 and ion-exchanged water were added. 284.24 parts was added, and it was placed in a heated oil bath and stirred. When the internal temperature was stabilized at 80 ° C., 0.1603 parts (0.5931 mmol) of potassium persulfate dissolved in 20 parts of ion-exchanged water was added and heated for 4 hours. A sample for measurement was prepared by evaporating water from the obtained liquid by evaporation. When the prepared measurement sample was subjected to NMR measurement using heavy DMF, it was confirmed that the polymerizable functional group of the benzimidazolinone derivative 1 did not react at 80 ° C.

  The reactivity of the polymerizable functional group was confirmed in the same manner as in the case of the benzimidazolinone derivative 1 except that the benzimidazolinone derivative 1 was changed to 0.2564 part (0.6410 mmol) of the benzimidazolinone derivative 2. did. As a result, it was confirmed that the polymerizable functional group of the benzimidazolinone derivative 2 did not react at 80 ° C.

  The reactivity of the polymerizable functional group was confirmed in the same manner as in the case of the benzimidazolinone derivative 1 except that the benzimidazolinone derivative 1 was changed to 0.2026 part (0.6410 mmol) of the benzimidazolinone derivative 3. did. As a result, it was confirmed that the polymerizable functional group of the benzimidazolinone derivative 3 did not react at 80 ° C.

  The reactivity of the polymerizable functional group was confirmed in the same manner as in the case of benzimidazolinone derivative 1 except that benzimidazolinone derivative 1 was changed to 0.2385 parts (0.6410 mmol) of benzimidazolinone derivative 4. did. As a result, it was confirmed that the polymerizable functional group of the benzimidazolinone derivative 4 did not react at 80 ° C.

<Preparation of resin fine particle dispersion>
(Example 1)
To a 300 mL four-necked flask equipped with a stirring seal, stirring rod, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 0.2115 parts (0.6410 mmol) of benzimidazolinone derivative 1, n-butyl 17.116 parts (1333.4758 mmol) of acrylate, 8.6079 parts (82.4691 mmol) of styrene, and 4.3073 parts (59.7738 mmol) of acrylic acid were added. After stirring and mixing, 284.24 parts of ion-exchanged water was added with stirring, and nitrogen flow was started. After replacing with nitrogen for 30 minutes, place in a heated oil bath, and when the internal temperature is stabilized at 80 ° C., add 0.1603 parts (0.5931 mmol) of potassium persulfate dissolved in 20 parts of ion-exchanged water. Polymerization was started. The polymerization was carried out while monitoring the polymerization status by gel permeation chromatography and NMR. The obtained reaction solution was filtered through an ultrafiltration membrane (manufactured by Toyo Roshi Kaisha, Ltd.) having a molecular weight cut off of 16,000. The filtrate was subjected to NMR measurement, and purification was performed by exchanging water until the peak of the residual monomer that did not react was detected. When the acid value of the obtained purified product was measured (measuring solvent: THF), it was 112 mgKOH / g. Further, after the purified product was concentrated with an evaporator, a 1 mol / L potassium hydroxide aqueous solution was added to adjust the pH to 8 to obtain a resin fine particle dispersion 1 (solid content concentration: 10%). The weight average molecular weight of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 1 was 200,000.

(Example 2)
Resin fine particle dispersion 2 (solid content concentration: 10%) in the same manner as in Example 1 except that benzimidazolinone derivative 1 was changed to 0.2564 part (0.6410 mmol) of benzimidazolinone derivative 2 ) The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 2 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 3)
Resin fine particle dispersion 3 (solid content concentration: 10%) in the same manner as in Example 1 except that benzimidazolinone derivative 1 was changed to 0.2026 part (0.6410 mmol) of benzimidazolinone derivative 3 ) The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 3 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

Example 4
Resin fine particle dispersion 4 (solid content concentration: 10%) in the same manner as in Example 1 except that benzimidazolinone derivative 1 was changed to 0.2385 parts (0.6410 mmol) of benzimidazolinone derivative 4 ) The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 4 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 5)
Resin fine particle dispersion 5 (solid content concentration: 10%) in the same manner as in Example 1 except that only 28.9632 parts (152.9268 mmol) of 2-methacryloyloxyethyl succinate was used as a monomer. Got. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 5 was 244 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 6)
Resin fine particle dispersion 6 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that only 4.3043 parts (23.3743 mmol) of 10-undecylenic acid was used as a monomer. . The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 6 was 304 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 7)
Resin fine particle dispersion 7 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that only 28.0000 parts (218.4087 mmol) of n-butyl acrylate was used as a monomer. . The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 7 was 0 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 8)
Resin fine particle dispersion 7 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that only 28.0000 parts (2688.830 mmol) of styrene was used as a monomer. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 7 was 0 mgKOH / g, and the weight average molecular weight was 200,000.

Example 9
Resin fine particle dispersion 9 was prepared in the same manner as in Example 1 except that 14.0000 parts (134.4215 mmol) of styrene and 14.0000 parts (109.2033 mmol) of n-butyl acrylate were used as monomers. (Solid content concentration: 10%) was obtained. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 9 was 0 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 10)
Resin fine particle dispersion 10 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that the amount of potassium persulfate was changed to 2.2674 parts (8.38779 mmol). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 10 was 112 mgKOH / g, and the weight average molecular weight was 1,000.

(Example 11)
Resin fine particle dispersion 11 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that the amount of potassium persulfate was changed to 0.0926 parts (0.3424 mmol). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 11 was 112 mgKOH / g, and the weight average molecular weight was 600,000.

(Example 12)
Resin fine particle dispersion 12 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that the amount of potassium persulfate was changed to 3.2066 parts (11.621 mmol). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 12 was 112 mgKOH / g, and the weight average molecular weight was 500.

(Example 13)
Resin fine particle dispersion 13 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that the amount of potassium persulfate was changed to 0.0889 parts (0.329 mmol). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 13 was 112 mgKOH / g, and the weight average molecular weight was 650,000.

(Example 14)
Water was added to the resin fine particle dispersion 1 obtained in Example 1 to obtain a resin fine particle dispersion 14 (solid content concentration: 3.0%). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 14 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 15)
The resin fine particle dispersion 1 obtained in Example 1 was evaporated to obtain a resin fine particle dispersion 15 (solid content concentration: 30%). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 15 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 16)
Water was added to the resin fine particle dispersion 1 obtained in Example 1 to obtain a resin fine particle dispersion 16 (solid content concentration: 2.5%). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 16 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 17)
The resin fine particle dispersion 1 obtained in Example 1 was evaporated to obtain a resin fine particle dispersion 17 (solid content concentration: 31%). The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 17 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 18)
Resin fine particle dispersion 18 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that acrylic acid was changed to 4.3073 parts (50.0325 mmol) of methacrylic acid. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 18 was 93 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 19)
Resin fine particle dispersion 19 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that styrene was changed to 8.6079 parts (72.8372 mmol) of 4-vinyltoluene. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 19 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 20)
Resin fine particle dispersion 20 (solid content concentration: 10%) was obtained in the same manner as in Example 1 except that n-butyl acrylate was changed to 17.1116 parts (170.9109 mmol) of methyl methacrylate. It was. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 20 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Example 21)
While concentrating the resin fine particle dispersion 1 obtained in Example 1, 152.12 parts of glycerin was gradually added to obtain a resin fine particle dispersion 21 (solid content concentration: 10%) in which water was replaced with glycerin. The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 21 was 112 mgKOH / g, and the weight average molecular weight was 200,000. The solid content concentration of the resin fine particle dispersion 21 was calculated from the following equation based on the mass before glycerol replacement and the mass after glycerol replacement.
Solid content [%]
= Solid content concentration before substitution 10.0% x (mass after substitution [g] / mass before substitution [g])

(Comparative Example 1)
Resin fine particle dispersion 22 (solid content concentration: 10%) in the same manner as in Example 1 except that benzimidazolinone derivative 1 was changed to 0.1667 parts (0.6410 mmol) of benzimidazolinone derivative 5 ) The acid value of the resin constituting the resin fine particles in the obtained resin fine particle dispersion 22 was 112 mgKOH / g, and the weight average molecular weight was 200,000.

(Comparative Example 2)
An attempt was made to prepare a resin fine particle dispersion in the same manner as in Example 1 except that only 26.7583 parts (371.3336 mmol) of acrylic acid was used as the monomer, but the formation of resin fine particles was confirmed. I could not. In addition, the acid value of the obtained resin was 779 mgKOH / g, and the weight average molecular weight was 200,000.

  Details of the resin fine particle dispersions obtained in Examples 1 to 21 and Comparative Examples 1 and 2 are shown in Table 1.

<Evaluation of resin fine particle dispersion>
(Adsorption to colorant)
[Sample preparation for measurement]
17 parts of ion exchange water and 14 parts of resin fine particle dispersion 14 were mixed to obtain a solution (S). To the obtained solution (S), 5.3 parts of carbon black (trade name “CAB-O-JET400”, manufactured by Cabot Corporation, solid content concentration: 15%) was added, and ultrasonic dispersion was performed for 30 minutes. After standing at room temperature for 1 hour, the supernatant was collected by centrifugation. The solution (S) and the supernatant were used as samples for measurement. In addition, samples for measurement of each resin fine particle dispersion were prepared in the same manner as described above except that the type and amount of the resin fine particle dispersion and the amount of ion-exchanged water were as shown in Table 2. . In addition, about the resin fine particle dispersion 23, since the formation of the resin fine particle was not confirmed, a sample for measurement was not prepared.

[Measurement and calculation of adsorption rate]
Ion exchanged water was added to the prepared solution (S) and the supernatant, respectively, and diluted 20 times to obtain a measurement solution (solution (S) dilution, supernatant dilution). The absorbance at 420 nm of each measurement solution was measured, and the adsorption rate of each resin fine particle dispersion to the coloring material was calculated from the following formula (I).
Adsorption rate (%) = (1−j / k) × 100 (I)
j: Absorbance of supernatant diluted solution k: Absorbance of solution (S) diluted solution

[Evaluation criteria]
From the calculated adsorption rate of each resin fine particle dispersion, the adsorptivity to the coloring material was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
○: Adsorption rate of 80% or more ×: Adsorption rate of less than 80%

(Dispersion stability)
For each resin fine particle dispersion, the volume cumulative median diameter of the resin fine particles was measured, and then stored in a sealed state for 2 weeks under a temperature condition of 80 ° C. The volume cumulative median diameter of the resin fine particles in the resin fine particle dispersion after storage was measured, and the particle diameter increase rate of each resin fine particle dispersion was calculated from the following formula (II). From the calculated particle diameter increase rate of each resin fine particle dispersion, the dispersion stability was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2. A nanoparticle size distribution measuring instrument (trade name “UPA-EX250”, manufactured by Nikkiso Co., Ltd.) was used for measuring the volume cumulative median diameter of resin fine particles.
Particle diameter increase rate (%) = {(A−B) / B} × 100 (II)
A: Volume cumulative median diameter of resin fine particles after storage B: Volume cumulative median diameter of resin fine particles before storage A: Particle diameter increase rate is 5% or less ○: Particle diameter increase rate is more than 5% and 10% or less Δ : Particle diameter increase rate is over 10% and 30% or less. ×: Particle diameter increase rate is over 30%.

  As is clear from the evaluation results shown in Table 2, the adsorptivity to the colorant and the dispersion stability of the resin fine particle dispersions of Examples 1 to 21 were both good. On the other hand, the resin fine particle dispersion of Comparative Example 1 had poor adsorptivity to the coloring material. Further, Comparative Example 2 could not be evaluated because the formation of resin fine particles could not be confirmed.

<Preparation of ink>
(Example 22)
10 parts of glycerin, 20 parts of diethylene glycol and 35 parts of ion-exchanged water were mixed, and a 1 mol / L potassium hydroxide aqueous solution added to adjust the pH to 7 was added dropwise to 15 parts of the stirred resin fine particle dispersion 1. After sufficiently stirring, the solution was added dropwise to 20 parts of stirred carbon black (trade name “CAB-O-JET400”, manufactured by Cabot Corporation, solid content concentration: 15%). A 1 mol / L aqueous potassium hydroxide solution was added to adjust the pH to 9, and then filtered through a filter having a pore size of 1.2 μm to obtain ink 1.

(Example 23)
Ink 2 was obtained in the same manner as in Example 22 except that carbon black was changed to Pigment Blue 15: 4 (trade name “CAB-O-JET450C”, manufactured by Cabot, solid content concentration: 15%). It was.

(Example 24)
Ink 3 was obtained in the same manner as in Example 22 except that carbon black was changed to Pigment Yellow 74 (trade name “CAB-O-JET470Y”, manufactured by Cabot Corporation, solid content concentration: 15%).

(Example 25)
Ink 4 was obtained in the same manner as in Example 22 except that the carbon black was changed to Pigment Red 122 (trade name “CAB-O-JET465M”, manufactured by Cabot Corporation, solid content concentration: 15%).

(Example 26)
Ink 5 was obtained in the same manner as in Example 22 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 2.

(Example 27)
Ink 6 was obtained in the same manner as in Example 22 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 3.

(Example 28)
An ink 7 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 4.

(Example 29)
Ink 8 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 5.

(Example 30)
Ink 9 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 6.

(Example 31)
An ink 10 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 7.

(Example 32)
Ink 11 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 8.

(Example 33)
An ink 12 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 9.

(Example 34)
An ink 13 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 10.

(Example 35)
An ink 14 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 11.

(Example 36)
An ink 15 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 12.

(Example 37)
Ink 16 was obtained in the same manner as in Example 22 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 13.

(Example 38)
Ink 17 was obtained in the same manner as in Example 22 except that ion-exchanged water was not used and that resin fine particle dispersion 1 was changed to 1450 parts of resin fine particle dispersion 1.

(Example 39)
Ink 18 was obtained in the same manner as in Example 22 except that 45 parts of ion-exchanged water was used and that resin fine particle dispersion 1 was changed to 155 parts of resin fine particle dispersion 1.

(Example 40)
Examples described above, except that ion-exchanged water was not used, and instead of resin fine particle dispersion 1, 50 parts of resin fine particle dispersion 16 concentrated by evaporation from 60 parts to 50 parts was used. In the same manner as in No. 22, ink 19 was obtained.

(Example 41)
Ink 20 was obtained in the same manner as in Example 22 except that 45.16 parts of ion-exchanged water was used and that resin fine particle dispersion 1 was changed to 4.8 parts of resin fine particle dispersion 17.

(Example 42)
An ink 21 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 18.

(Example 43)
An ink 22 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 19.

(Example 44)
An ink 23 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 20.

(Example 45)
Ink 24 was used in the same manner as in Example 22 except that 2.6 parts of glycerin, 28 parts of ion-exchanged water were used, and resin fine particle dispersion 1 was changed to resin fine particle dispersion 21. Got.

(Comparative Example 3)
An ink 25 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 22.

(Comparative Example 4)
An ink 26 was obtained in the same manner as in Example 22 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 23.

<Evaluation of ink>
(Dispersion stability)
The dispersion stability of the ink was evaluated by the same method as the “dispersion stability” in the “evaluation of resin fine particle dispersion” described above. The evaluation results are shown in Table 3.

(Abrasion resistance)
Each ink was mounted on an ink jet recording apparatus, and after printing a 100% duty solid image on a recording medium, the ink was left at 25 ° C. for 24 hours. The printing surface of the recording medium was rubbed 50 times with Sylphone paper applied with a load of 2 × 10 ⁴ N / m ² . Then, the transfer state of the printed portion (solid image) on the Sylphone paper was visually confirmed, and the scratch resistance of the image was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 3. As the ink jet recording apparatus, a thermal type ink jet recording apparatus (trade name “P-660CII”, manufactured by Canon Finetech Co., Ltd.) that discharges ink by applying thermal energy was used. Further, plain paper (trade name “GF-500”, manufactured by Canon Inc.) was used as the recording medium.
○: Image is not rubbed and does not adhere to sylbon paper △: Image is not rubbed but adheres to sylbon paper ×: Image is slightly rubbed −: Cannot be ejected or cannot be measured

  The inks of Examples 22 to 45 had good dispersion stability and scratch resistance after printing. On the other hand, the ink of Comparative Example 3 had poor scratch resistance after printing and was unusable as an ink.

  The resin fine particle dispersion of the present invention can be suitably used as a binder that can be added to ink jet recording ink. If the ink for ink jet recording of the present invention is used, an image excellent in scratch resistance can be recorded even on paper having low ink permeability such as coated printing paper.

100: ink cartridge 101: ink bag 102: rubber stopper 103: needle 104: tube 201: base plate 202: ink nozzle (discharge port)
203: Partition 204: Nozzle heater 205: Common liquid chamber 206: Substrate 207: Top plate 300: Recording device 301: Roll supply unit 302: Recording medium (roll paper)
303: Recording head (black)
304: Recording head (cyan)
305: Recording head (magenta)
306: Recording head (yellow)
307: Ink cartridge (black)
308: Ink cartridge (cyan)
309: Ink cartridge (magenta)
310: Ink cartridge (yellow)
311: Cap mechanism 312: Conveying motor 313: Conveying belt 400: Cap 401: Sub tank 402: Pressurizing pump 403: Suction pump 404 a: Supply valve 404 b: Recovery valve 404 c: Atmospheric release valve 404 d: Recycling valve 405: Filter 406: Face (Nozzle) surface 80: ink flow path 81: orifice plate 82: diaphragm 83: piezoelectric element 84: substrate 85: discharge port

Claims (11)

A resin fine particle dispersion comprising: an aqueous medium; and resin fine particles surface-modified with a benzimidazolinone derivative represented by the following general formula (1) dispersed in the aqueous medium.

(In the general formula (1), Z ₁ and Z _k each independently represent a methyl group or a polymerizable functional group, provided that at least one of Z ₁ and Z _k is a polymerizable functional group). The resin fine particle dispersion according to claim 1, wherein the benzimidazolinone derivative is represented by the following formula (1-1).

The resin fine particle is a structural unit A derived from at least one of the monomer (A-1) represented by the following general formula (2) and the monomer (A-2) represented by the following general formula (3); The resin fine particle dispersion according to claim 1 or 2, wherein raw material fine particles comprising a copolymer having a structural unit B derived from the monomer (B-1) represented by the general formula (4) is surface-modified. body.
^{_{CH 2 = CR 1 -COO- (CH}} 2 -CH 2 -O) m -R 2 ··· (2)
(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heteroaromatic hydrocarbon. And m represents an integer of 0 to 2)
^{_{CH 2 = CR 3 -Ar-R}} 4 ··· (3)
(In the general formula (3), R ³ represents a hydrogen atom or a methyl group, Ar represents a phenylene group, R ⁴ represents a hydrogen atom, —R ⁵ , —OR ⁵ , or —COOR ⁵ . And R ⁵ represents an alkyl group having 1 to 18 carbon atoms)
^{_{CH 2 = CR 6 -X-COOH}} ··· (4)
(In the general formula (4), R ⁶ represents a hydrogen atom or a methyl group, and X represents a single bond or a linear alkylene group having 1 to 9 carbon atoms, provided that in the linear alkylene group, —CH ₂ — may be substituted with —O—, —COO—, or —OCO— under the condition that no —O—O— bond occurs. The structural unit A is a structural unit derived from at least one selected from the group consisting of styrene, n-butyl acrylate, methyl methacrylate, and vinyl toluene,
The resin fine particle according to claim 3, wherein the structural unit B is a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, 10-undecylenic acid, and 2-methacryloyloxyethyl succinate. Dispersion.   The resin fine particle dispersion according to any one of claims 1 to 4, wherein a content of the resin fine particles is 3 to 30% by mass.   The resin fine particle dispersion according to any one of claims 1 to 5, wherein the aqueous medium is water.   An ink for ink jet recording comprising the resin fine particle dispersion according to any one of claims 1 to 6, a colorant, and a water-soluble organic solvent. An ink jet recording method including a step of applying to a recording medium ink that has been ejected by applying energy,
An ink jet recording method, wherein the ink is the ink for ink jet recording according to claim 7.   The ink jet recording method according to claim 8, wherein the energy is thermal energy. An ink cartridge comprising an ink containing portion containing ink,
An ink cartridge, wherein the ink is an ink jet recording ink according to claim 7. An ink jet recording apparatus comprising: an ink cartridge having an ink containing portion containing ink; and a head portion for discharging the ink,
An ink jet recording apparatus, wherein the ink is an ink for ink jet recording according to claim 7.

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