JP6452317B2 - Resin fine particle dispersion, ink for ink jet recording, ink jet recording method, ink cartridge, and ink jet recording apparatus - Google Patents

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 when dispersing resin fine particles in an aqueous medium, a polymer dispersion that is a copolymer having a specific structural unit having a benzimidazolinone skeleton The present inventors have found that the above problems can be solved by using an agent, and have completed the present invention.

That is, according to the present invention, the following resin fine particle dispersion is provided.
[1] A benzimidazolinone containing an aqueous medium and resin fine particles dispersed in the aqueous medium with a polymer dispersant, wherein the polymer dispersant is represented by the following general formula ( 1-1 ) A structural unit P derived from a derivative, a structural unit A derived from at least one of a monomer represented by the following general formula (2) and a monomer represented by the following general formula (3), and the following general formula (4) A structural unit B derived from the monomer represented by formula (1), wherein the resin fine particles are a monomer represented by the following general formula (2) and a monomer represented by the following general formula (3). A resin fine particle dispersion which is formed of a copolymer having a structural unit A derived from at least one of them.

^{_{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.

[ 2 ] 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 [1 ], 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.
[ 3 ] The resin fine particle dispersion according to [1] or [2] , wherein the polymer dispersant has a weight average molecular weight of 1,000 to 50,000.
[ 4 ] The resin fine particle dispersion according to any one of [1] to [ 3 ], wherein the polymer dispersant has an acid value of 30 to 120 mgKOH / g.
[ 5 ] The resin fine particles are structural units A derived from at least one of a monomer represented by the following general formula (2) and a monomer represented by the following general formula (3), and the following general formula (4): Any one of the above-mentioned [1] to [ 4 ], which is formed of a copolymer having a structural unit B derived from the represented monomer and having a weight average molecular weight of 1,000 to 600,000. 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.
[ 6 ] The resin fine particle dispersion according to any one of [1] to [ 5 ], wherein the resin fine particle content is 3 to 30% by mass.
[ 7 ] The resin fine particle dispersion according to any one of [1] to [ 6 ], wherein the aqueous medium is water.

Moreover, according to this invention, the ink for inkjet recording shown below is provided.
[ 8 ] An ink for inkjet recording, comprising the resin fine particle dispersion according to any one of [1] to [ 7 ], 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.
[ 9 ] 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 [ 8 ]. Inkjet recording method.
[ 10 ] The inkjet recording method according to [ 9 ], wherein the energy is thermal energy.
[ 11 ] An ink cartridge comprising an ink containing portion containing ink, wherein the ink is the ink for ink-jet recording described in [ 8 ].
[ 12 ] An ink jet recording apparatus including an ink cartridge including an ink storage portion that stores ink, and a head portion that discharges the ink, wherein the ink is for ink jet recording according to the above [ 8 ]. 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 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 dispersed in the aqueous medium with a polymer dispersant. The details will be described below.

(Polymer dispersant)
The polymer dispersant used in the resin fine particle dispersion of the present invention includes a structural unit P derived from a benzimidazolinone derivative represented by the general formula (1), a monomer represented by the general formula (2), and a general formula ( It is a copolymer having a structural unit A derived from at least one of the monomers represented by 3) and a structural unit B derived from the monomer represented by the general formula (4). This polymer dispersant has an affinity for an aqueous medium, an affinity for resin fine particles, and an adsorbing ability to a coloring material. In addition, since this polymer dispersing agent has a moderate acid value, the affinity to an aqueous medium is provided. Moreover, since it has the same structural unit A and B as the structural unit contained in the copolymer which comprises resin microparticles | fine-particles, the affinity to resin microparticles | fine-particles is provided. Further, since it has a benzimidazolinone skeleton, an acetylacetone skeleton, and a diazo moiety, it has an ability to adsorb to a coloring material.

  The acid value of the polymer dispersant is preferably 30 to 120 mgKOH / g. The acid value of the polymer dispersant (copolymer) is represented by the amount (mg) of KOH required to neutralize 1 g of the copolymer. In a thermal ink jet recording method that records an image by applying ink that has been ejected by applying thermal energy to a recording medium, discharge is stable when the acid value of the polymer dispersant is 30 mgKOH / g or more. There is a tendency. On the other hand, when the acid value of the polymer dispersant is 120 mgKOH / g or less, solubility in an aqueous medium is suppressed. For this reason, the polymer dispersant tends to stay on the surface of the resin fine particles, and the ejection tends to be stable. The acid value of the polymer dispersant can be calculated from the composition ratio of each monomer constituting the polymer dispersant, but is measured by potentiometric titration using a trade name “Titrino” (manufactured by Metrohm) or the like. You can also.

[Benz imidazolinone derivatives]
A benzimidazolinone derivative is a compound represented by the following general formula (1).

（前記一般式（１）中、Ｚ_ｎは、水素原子又は２−（メタ）アクリロイルオキシエチル基を示し、Ｚ_ｍは、メチル基又は（メタ）アクリロイルオキシ基を示す。但し、Ｚ_ｎ及びＺ_ｍの少なくとも一方は（メタ）アクリロイルオキシ基を含む）

(In the general formula (1), _{Z n} represents a hydrogen atom or a 2- (meth) acryloyloxyethyl group, _{Z m} represents a methyl group or a (meth) acryloyloxy groups. However, _{Z n} and Z at least one of _m contains a (meth) acryloyloxy 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, the polymer dispersant having the structural unit P derived from the benzimidazolinone derivative is excellent in the adsorption performance to the 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) and (2).

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.

[Structural unit A]
The structural unit A is a structural unit derived from at least one of the monomer represented by the following general formula (2) and the monomer represented by the following general formula (3). In addition, the monomer represented by following General formula (2) is (meth) acrylic acid ester and its derivative (s), for example. Moreover, the monomer 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 represented by the general formula (2) include (meth) acrylic acid such as methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methyl acrylate, isopropyl acrylate, and n-butyl acrylate. Esters (m = 0); ethoxyalkyl (meth) acrylates such as 2-ethoxyethyl methacrylate and 2-ethoxyethyl acrylate (m = 1); 2- (2-ethoxyethoxy) ethyl methacrylate, acrylic And (meth) acrylic acid ethoxyethoxyalkyls such as 2- (2-ethoxyethoxy) ethyl acid (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 a monomer represented by the following general formula (4). The monomer represented by the following general formula (4) is a monomer having a carboxy group at its end.

^{_{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 represented by the general formula (4) 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.

  When the copolymer which is a polymer dispersant is composed only of the structural unit A, the adhesion between the resin fine particles and the recording medium is poor. Moreover, when the copolymer which is a polymer dispersing agent is comprised only with the structural unit B, since water solubility is too high, water resistance is inferior. For this reason, it is preferable that the polymer dispersant (copolymer) used for the resin fine particle dispersion of the present invention 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 content of the structural unit P in the polymer dispersant is preferably 1 to 12 mol%. When the content of the structural unit P in the polymer dispersant is 1 mol% or more, the recorded image tends to have better scratch resistance. On the other hand, when the content of the structural unit P in the polymer dispersant is 12 mol% or less, the solubility of the polymer dispersant becomes better, so that the dispersion stability of the resin fine particles tends to be further improved. . The content of the structural unit P in the polymer dispersant can be calculated from the following formula (I).
Content of structural unit P (mol%) = 100 × {p / (p + a + b)} (I)
p: Number of structural units P in the polymer dispersant (mol)
a: Number (mol) of structural unit A in the polymer dispersant
b: Number of structural units B in the polymer dispersant (mol)

  The weight average molecular weight of the polymer dispersant is preferably 1,000 to 50,000. A polymer dispersant having a weight average molecular weight of 1,000 or more is less likely to be released in the film after coating. On the other hand, by using a polymer dispersant having a weight average molecular weight of 50,000 or less, the dispersibility of the resin fine particles can be improved. A polymer dispersant having the same structural units A and B as the structural units contained in the copolymer constituting the resin fine particles is preferable because of its excellent affinity for the resin fine particles.

(Method for synthesizing polymer dispersant)
The polymer dispersant can be synthesized by a conventionally known polymerization method such as radical polymerization, living radical polymerization, or anionic polymerization. Synthesis conditions such as reaction temperature, reaction time, reaction solvent, and catalyst; termination conditions, purification method after synthesis, and the like are not particularly limited, and can be appropriately selected according to the target product. In the polymer dispersant used for the resin fine particle dispersant of the present invention, the structural unit P, the structural unit A, and the structural unit B may exist in a random state or may exist in a block state. The synthesized polymer dispersant can be identified by qualitative and quantitative determination of functional groups by NMR or IR, analysis by various chromatographies, and the like.

(Resin fine particles)
The resin fine particle dispersion of the present invention contains resin fine particles dispersed in an aqueous medium by the polymer dispersant. The resin fine particles are preferably formed of a copolymer having the structural unit A and the structural unit B.

[Structural unit A]
The structural unit A is a structural unit derived from at least one of the monomer represented by the following general formula (2) and the monomer represented by the following general formula (3). In addition, the monomer represented by following General formula (2) is (meth) acrylic acid ester and its derivative (s), for example. Moreover, the monomer 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 represented by the general formula (2) include (meth) acrylic acid such as methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methyl acrylate, isopropyl acrylate, and n-butyl acrylate. Esters (m = 0); ethoxyalkyl (meth) acrylates such as 2-ethoxyethyl methacrylate and 2-ethoxyethyl acrylate (m = 1); 2- (2-ethoxyethoxy) ethyl methacrylate, acrylic And (meth) acrylic acid ethoxyethoxyalkyls such as 2- (2-ethoxyethoxy) ethyl acid (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 a monomer represented by the following general formula (4). The monomer represented by the following general formula (4) is a monomer having a carboxy group at its end.

^{_{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 represented by the general formula (4) 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 resin fine particles has only the structural unit A, the adhesion between the resin fine particles and a recording medium such as coated paper may be lowered. On the other hand, when the copolymer forming the resin 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 represented by the general formula (4), and the resin fine particles May not be 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 resin 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 ratio of the structural unit A to the structural unit B in the copolymer forming the resin fine particles can be arbitrarily set so that the acid value of the copolymer is preferably within the range described later.

  The weight average molecular weight of the copolymer forming the resin 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 polymer dispersant are placed in a 300 mL four-necked flask equipped with a stirring seal, a stirring bar, a reflux condenser, a septum rubber, and a nitrogen introduction tube, and purged with nitrogen 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 polymer dispersant is adsorbed on the surface of the raw material fine particles formed by polymerization by adding a predetermined polymer dispersant in the polymerization system, and the polymer dispersant is at the interface between the resin fine particles and the aqueous medium. Is presumed to have played the same role as the surfactant.

  When ion-exchanged water is added to a mixture of a predetermined monomer and polymer dispersant, the polymer dispersant functions as an emulsifier having surface activity and is present 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. Resin fine particles are formed with the growth of the reaction product (copolymer), and a polymer dispersant of the formed resin fine particles and an aqueous medium is present.

  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 to 900 nm. Depending on the glass transition temperature of the copolymer constituting the resin fine particles, the thermal ink jet recording method for recording an image by applying thermal energy to the recording medium and recording the image on the recording medium, When the volume cumulative median diameter is less than 80 nm, ejection 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 copolymer constituting the resin fine particles is preferably 0 to 304 mgKOH / g. The acid value of the copolymer is represented by the amount (mg) of KOH required to neutralize 1 g of the copolymer. When the acid value of the copolymer 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 copolymer can be calculated from the composition ratio of each monomer constituting the copolymer, but can also be measured by potentiometric titration using a trade name “Titrino” (manufactured by Metrohm) or the like. it can.

  The acid value of the copolymer constituting the resin fine particles and the acid value of the above-described polymer dispersant can be arbitrarily set within respective preferable ranges. In addition, when the copolymer which comprises resin fine particles contains the structural unit B, neutralizing the carboxy group in the structural unit B with a base increases the electronic repulsion between copolymers, and resin fine particles The dispersion stability of can be further increased. 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. Moreover, it can be set as a low-viscosity ink as the content rate of a coloring material is 5 mass% or less.

  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.

  The structural unit P has a benzimidazolinone skeleton, an acetylacetone skeleton, and a diazo moiety. For this reason, the polymer dispersant having the structural unit P is easily adsorbed to the coloring material. Therefore, the polymer dispersant is preferably 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 dispersed with a polymer dispersant and a coloring material in the liquid. This is presumably due to the following reasons.

  The structural unit P in the polymer dispersant has a number of —NH— groups in its structure, 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 polymer dispersant and the color material is inhibited by water molecules. Therefore, in the water-based ink, the resin fine particles dispersed with the polymer dispersant The dispersion stability of is maintained.

  The resin fine particles and the color material dispersed with the polymer dispersant may be present in the same ink, or may be present 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, the water molecules that hinder the adsorption of the structural unit P and the color material in the polymer dispersant are reduced, thereby reducing the distance between the structural unit P and the color material in the polymer dispersant. It is thought that adsorption of fine particles and coloring material occurs.

(Coloring 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 polymer dispersant used in the resin fine particle dispersion of the present invention exhibits excellent adsorption performance for any of these coloring materials.

  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. In the ink of the present invention, the above-mentioned pigment and oil-soluble dye can be used alone or in an appropriate mixture.

(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 (Mw) of the copolymer and the polymer dispersant constituting the resin fine particles is GPC (trade name “HLC8220” manufactured by Tosoh Corporation, column: TSK-GEL4000HXL, TSK-GEL3000HXL, TSK-GEL2000HXL, column oven) Temperature: 40.0 ° C.). The acid value of the copolymer and the polymer dispersant constituting the resin fine particles is determined by an automatic titration apparatus (trade name “Titrino”, Metrohm) according to the acid value measurement method by potentiometric titration described in Japanese Industrial Standard JIS-K0070. Manufactured, solvent: tetrahydrofuran). Further, the volume cumulative median diameter of the resin fine particles was measured using a particle size distribution measuring apparatus (trade name “FPAR-1000”, manufactured by Otsuka Electronics Co., Ltd., calculation method: cumulant method) using a laser scattering method.

<Synthesis of Intermediate 1>
To a 1 L four-necked flask equipped with a stirring seal, stirring rod, dropping funnel, septum rubber, nitrogen inlet tube, and thermometer, 14 parts (0.1 mol) of 2- (4-aminophenyl) ethanol 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, to 23 parts (0.1 mol) of 5- (acetoacetamido) -2-benzimidazolinone, 230 parts of ethanol and 126 parts (0.56 mol) of a 36.5% aqueous sodium acetate solution were added and stirred. The solution was prepared by cooling to 5 ° C. or lower. 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 Intermediate 1 (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, 15.2 parts (0.04 mol) of intermediate 1 obtained above and pyridine 170 were obtained. The intermediate 1 was dissolved in pyridine and cooled to 5 ° C. or lower. Subsequently, 12.5 parts (0.12 mol) of methacryloyl chloride dissolved in 90 parts of pyridine was added dropwise and stirred for 1 hour. Thereafter, 200 parts of water was added to stop the reaction, and separation by centrifuging and washing with water were performed to obtain a benzimidazolinone derivative 1 represented by the formula (1-1) (yield 73%).

<Synthesis of Intermediate 2>
To a 1 L four-necked flask equipped with a stirring seal, stirring rod, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 104 parts (1 mol) of malonic acid, 5-amino-2-benzimidazolinone 15 Part (0.1 mol) and 300 parts of THF were added and heated under reflux for 2 hours with stirring. Thereafter, the solvent was distilled off, and the resulting precipitate was washed with water and dried to obtain Intermediate 2 (yield 95%).

<Synthesis of Intermediate 3>
2- (4-aminophenyl) ethanol was changed to 9 parts (0.1 mol) of aniline, and 5- (acetoacetamido) -2-benzimidazolinone was replaced with 24 parts (0.1 mol) of intermediate 2 The intermediate 3 was synthesized by the same method as the above-mentioned “Synthesis of the intermediate 1” except that the yield was 49%.

<Synthesis of benzimidazolinone derivative 2>
Benzimidazolinone derivative 2 was synthesized in the same manner as in the above-mentioned “Synthesis of benzimidazolinone derivative 1” except that intermediate 1 was changed to 13.6 parts (0.04 mol) of intermediate 3 (0.04 mol) ( Yield 73%).

<Synthesis of Intermediate 4>
Intermediate 4 was synthesized by the same method as “Synthesis of Intermediate 3” described above, except that aniline was changed to 2- (4-aminophenyl) ethanol (yield 49%).

<Synthesis of benzimidazolinone derivative 3>
Benzimidazolinone derivative 3 was synthesized in the same manner as in “Synthesis of benzimidazolinone derivative 1” described above except that Intermediate 1 was changed to 15.3 parts (0.04 mol) of Intermediate 4 (0.04 mol) ( Yield 73%).

<Synthesis of polymer dispersant>
(Polymer dispersant 1)
Into a 300 mL four-necked flask equipped with a stirring seal, stirring rod, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 6.8890 parts (15.2924 mmol) of benzimidazolinone derivative 1 and acrylic acid n -17.116 parts (1333.4758 mmol) of butyl, 8.6094 parts (82.6633 mmol) of styrene, 5.3613 parts (74.4088 mmol) of acrylic acid and 284.24 parts of dimethylformamide. After stirring and mixing, a nitrogen flow was started. After substituting with nitrogen for 30 minutes, it was placed in a heated oil bath, and when the internal temperature was stabilized at 120 ° C., an azo polymerization initiator dissolved in 20 parts of dimethylformamide (trade name “VAm-110”, Wako Pure Chemical Industries, Ltd.) Polymerization was started by adding 0.6128 parts (1.9613 mmol). The polymerization was carried out while monitoring the polymerization status by gel permeation chromatography and NMR. The obtained reaction solution was purified by dialysis with an ultrafiltration membrane (manufactured by Toyo Roshi Kaisha, Ltd.) having a molecular weight cut off of 16,000. The solvent contained in the purified product obtained using an evaporator was distilled off to obtain a polymer dispersant 1. The weight average molecular weight of the obtained polymer dispersant 1 was calculated by ¹ H-NMR (measurement solvent: N, N-dimethylformamide-d7) and GPC (developing solvent: tetrahydrofuran). Further, the UV absorption amount at 420 nm of the polymer dispersant 1 was measured using a spectrophotometer (trade name “U-3310” manufactured by Hitachi, Ltd.), and the content (mol%) of the structural unit P was calculated. . Furthermore, the acid value was measured using tetrahydrofuran as a measurement solvent. As a result, the obtained polymer dispersant 1 had a weight average molecular weight (Mw) of 20,000, an acid value of 110 mgKOH / g, and a content of the structural unit P of 5 mol%.

(Polymer dispersant 2)
The benzimidazolinone derivative 1 was changed to 6.8990 parts (15.2919 mmol) of the benzimidazolinone derivative 2, the amount of styrene was changed to 8.6051 parts (82.6224 mmol), and the amount of acrylic acid was changed. The above-mentioned “polymer dispersing agent” except that the amount was changed to 5.3656 parts (74.4598 mmol) and the amount of the trade name “VAm-110” was changed to 0.6130 parts (1.9621 mmol). The polymer dispersant 2 was obtained in the same manner as in “1”. Table 1 shows various physical property values of the obtained polymer dispersant 2.

(Polymer dispersant 3)
The benzimidazolinone derivative 1 was changed to 8.6128 parts (15.926 mmol) of the benzimidazolinone derivative 3, the amount of styrene was changed to 8.3630 parts (80.2978 mmol), and the amount of acrylic acid was changed to Except for the change to 5.6077 parts (77.8197 mmol) and the amount of the trade name “VAm-110” was changed to 0.6267 parts (2.0058 mmol), the above-mentioned “polymer dispersant” The polymer dispersant 3 was obtained in the same manner as in “1”. Table 1 shows various physical property values of the obtained polymer dispersant 3.

(Polymer dispersant 4)
The amount of benzimidazolinone derivative 1 was changed to 5.6607 parts (mmol), the acrylic acid was changed to 19.6841 parts (85.5832 mmol) of 2-methacryloyloxyethyl succinate, the amount of styrene was 6 1289 parts (58.8468 mmol), the amount of n-butyl acrylate was changed to 12.1815 parts (95.0193 mmol), and the amount of the trade name “VAm-110” was changed to 0.1. Except for changing to 6572 parts (2.1035 mmol), Polymer Dispersant 4 was obtained in the same manner as in “Polymer Dispersant 1” described above. Table 1 shows various physical property values of the obtained polymer dispersant 4.

(Polymer dispersant 5)
The amount of benzimidazolinone derivative 1 was changed to 5.7974 parts (12.69069 mmol), acrylic acid was changed to 14.4919 parts (78.6408 mmol) of 10-undecylenic acid, and the amount of styrene was 6 6364 parts (63.7196 mmol), the amount of n-butyl acrylate was changed to 13.1882 parts (102.8722 mmol), and the amount of the trade name “VAm-110” was changed to 0.8. Except for changing to 6300 parts (2.0164 mmol), Polymer Dispersant 5 was obtained in the same manner as in “Polymer Dispersant 1” described above. Various physical property values of the resulting polymer dispersant 5 are shown in Table 1.

(Polymer dispersant 6)
The amount of benzimidazolinone derivative 1 was changed to 6.5819 parts (14.6534 mmol), the acrylic acid was changed to 6.2961 parts (73.1341 mmol) of methacrylic acid, and the amount of styrene was 8.1846. Parts (788.5848 mmol), the amount of n-butyl acrylate was changed to 16.2424 parts (126.6960 mmol), and the amount of the trade name “VAm-110” was 0.6076 parts. Except for the change to (1.9445 mmol), a polymer dispersant 6 was obtained in the same manner as in the above-mentioned “polymer dispersant 1”. Various physical property values of the obtained polymer dispersant 6 are shown in Table 1.

(Polymer dispersant 7)
The amount of benzimidazolinone derivative 1 was changed to 6.6365 parts (14.7751 mmol), styrene was changed to 8.281 parts (73.0078 mmol) of vinyl toluene, and the amount of n-butyl acrylate was changed. It was changed to 17.1443 parts (133.7308 mmol), the amount of acrylic acid was changed to 5.3315 parts (73.9776 mmol), and the amount of the trade name “VAm-110” was 0.6111 parts. Except for the change to (1.9558 mmol), Polymer Dispersant 7 was obtained in the same manner as in “Polymer Dispersant 1” described above. Various physical property values of the obtained polymer dispersant 7 are shown in Table 1.

(Polymer dispersant 8)
N-Butyl acrylate was changed to 16.9856 parts (169.6526 mmol) of methyl methacrylate, the amount of styrene was changed to 8.5460 parts (82.0548 mmol), and the amount of acrylic acid was changed to 5. “Polymer Dispersant 1” described above except that it was changed to 4760 parts (75.9919 mmol) and the amount of the trade name “VAm-110” was changed to 0.6193 parts (1.9821 mmol). The polymer dispersant 8 was obtained in the same manner as in the above. Table 1 shows various physical property values of the obtained polymer dispersant 8.

(Polymer dispersant 9)
A polymer dispersant 9 was obtained in the same manner as in the case of the “polymer dispersant 1” except that the amount of the trade name “VAm-110” was changed to 2.7405 parts (8.7711 mmol). . Various physical property values of the resulting polymer dispersant 9 are shown in Table 1.

(Polymer dispersant 10)
A polymer dispersant 10 was obtained in the same manner as in the case of the “polymer dispersant 1” except that the amount of the trade name “VAm-110” was changed to 0.3876 parts (1.2402 mmol). . Table 1 shows various physical property values of the obtained polymer dispersant 10.

(Polymer dispersant 11)
A polymer dispersant 11 was obtained in the same manner as in the case of the “polymer dispersant 1” except that the amount of the trade name “VAm-110” was changed to 3.8757 parts (12.4042 mmol). . Various physical property values of the resulting polymer dispersant 11 are shown in Table 1.

(Polymer dispersant 12)
A polymer dispersant 12 was obtained in the same manner as in the case of the “polymer dispersant 1” except that the amount of the trade name “VAm-110” was changed to 0.3695 parts (1.1828 mmol). . Various physical property values of the resulting polymer dispersant 12 are shown in Table 1.

(Polymer dispersant 13)
The amount of n-butyl acrylate was changed to 21.2905 parts (166.0727 mmol), the amount of styrene was changed to 10.71119 parts (102.8512 mmol), and the amount of acrylic acid was 1.5576. Parts (21.6159 mmol) and the amount of the trade name “VAm-110” was changed to 0.6325 parts (2.0243 mmol). In the same manner as in the case, a polymer dispersant 13 was obtained. Table 1 shows various physical property values of the obtained polymer dispersant 13.

(Polymer dispersant 14)
The amount of n-butyl acrylate was changed to 16.6250 parts (129.6798 mmol), the amount of styrene was changed to 8.3646 parts (80.3126 mmol), and the amount of acrylic acid was 5.8042. Parts of (Polymer Dispersant 1) described above except that the amount of the product name “VAm-110” was changed to 0.6105 parts (1.9538 mmol). In the same manner as in the case, a polymer dispersant 14 was obtained. Various physical property values of the resulting polymer dispersant 14 are shown in Table 1.

(Polymer dispersant 15)
The amount of n-butyl acrylate was changed to 21.8516 parts (170.4491 mmol), the amount of styrene was changed to 10.9942 parts (105.5615 mmol), and the amount of acrylic acid was changed to 1.0470. Parts (14.5292 mmol) and the amount of the trade name “VAm-110” was changed to 0.6351 parts (2.0326 mmol). In the same manner as in the case, a polymer dispersant 15 was obtained. Table 1 shows various physical property values of the obtained polymer dispersant 15.

(Polymer dispersant 16)
The amount of n-butyl acrylate was changed to 16.1457 parts (125.9413 mmol), the amount of styrene was changed to 8.1234 parts (77.9972 mmol), and the amount of acrylic acid was 6.2405. Parts of the above-mentioned “Polymer Dispersant 1” except that the amount of the product name “VAm-110” was changed to 0.6082 parts (1.9464 mmol). In the same manner as in the case, a polymer dispersant 16 was obtained. Table 1 shows various physical property values of the obtained polymer dispersant 16.

(Polymer dispersant 17)
The amount of benzimidazolinone derivative 1 was changed to 1.3182 parts (2.9348 mmol), the amount of n-butyl acrylate was changed to 17.9005 parts (139.6293 mmol), and the amount of styrene. It was changed to 9.0063 parts (866.4744 mmol), the amount of acrylic acid was changed to 4.6433 parts (64.361 mmol), and the amount of the trade name “VAm-110” was 0.5703 parts. Except having changed to (1.8252 mmol), the polymer dispersing agent 17 was obtained like the above-mentioned "polymer dispersing agent 1". Table 1 shows various physical property values of the obtained polymer dispersant 17.

(Polymer dispersant 18)
The amount of benzimidazolinone derivative 1 was changed to 17.7957 parts (39.6192 mmol), the amount of n-butyl acrylate was changed to 15.5586 parts (121.3618 mmol), and the amount of styrene was changed. It was changed to 7.8280 parts (75.6111 mmol), the amount of acrylic acid was changed to 6.7749 parts (94.0170 mmol), and the amount of the trade name “VAm-110” was 0.6889 parts. Except for the change to (2.2047 mmol), a polymer dispersant 18 was obtained in the same manner as in the above-mentioned “polymer dispersant 1”. Table 1 shows various physical property values of the obtained polymer dispersant 18.

(Polymer dispersant 19)
The amount of benzimidazolinone derivative 1 was changed to 0.6558 parts (1.4600 mmol), the amount of n-butyl acrylate was changed to 17.9946 parts (140.3637 mmol), and the amount of styrene. It was changed to 9.0537 parts (86.9292 mmol), the amount of acrylic acid was changed to 4.5576 parts (63.2469 mmol), and the amount of the trade name “VAm-110” was 0.5650 parts. Except for the change to (1.4600 mmol), a polymer dispersant 19 was obtained in the same manner as in the above-mentioned “polymer dispersant 1”. Table 1 shows various physical property values of the obtained polymer dispersant 19.

(Polymer dispersant 20)
The amount of benzimidazolinone derivative 1 was changed to 19.5003 parts (43.4142 mmol), the amount of n-butyl acrylate was changed to 15.3163 parts (119.4720 mmol), and the amount of styrene was changed. 7.7061 parts (73.9907 mmol) were changed, the amount of acrylic acid was changed to 6.9954 parts (97.0771 mmol), and the amount of the trade name “VAm-110” was 0.7000 parts. Except for the change to (2.2403 mmol), a polymer dispersant 20 was obtained in the same manner as in the above-mentioned “polymer dispersant 1”. Table 1 shows various physical property values of the obtained polymer dispersant 20.

(Polymer dispersant 21)
The amount of benzimidazolinone derivative 1 was changed to 4.7434 parts (10.5605 mmol), the amount of n-butyl acrylate was changed to 18.8185 parts (1466.7902 mmol), and the amount of styrene. It was changed to 0 part (0 mmol), the amount of acrylic acid was changed to 3.8761 parts (53.7906 mmol), and the amount of the trade name “VAm-110” was 0.5211 parts (1.6676). Except for the change to (mmol), a polymer dispersant 21 was obtained in the same manner as in the case of the “polymer dispersant 1” described above. Table 1 shows various physical property values of the obtained polymer dispersant 21.

(Polymer dispersant 22)
The amount of the polymeric dispersant 1 was changed to 0 part (0 mmol), the amount of n-butyl acrylate was changed to 18.0878 parts (141.0907 mmol), and the amount of styrene was 9.1006 parts. (87.3795 mmol), the amount of acrylic acid was changed to 4.4723 parts (62.0696 mmol), and the amount of the trade name “VAm-110” was 0.5597 parts (1.7914). Except for the change to (mmol), a polymer dispersant 22 was obtained in the same manner as in the above-mentioned “polymer dispersant 1”. Table 1 shows various physical property values of the obtained polymer dispersant 22.

<Preparation of resin fine particle dispersion>
Example 1
In a 300 mL four-necked flask equipped with a stirring seal, a stirring bar, a reflux condenser, a septum rubber, a nitrogen introduction tube, and a thermometer, 3.1082 parts (0.1554 mmol) of polymer dispersant 1 and ion-exchanged water 284.24 parts were added. After mixing, nitrogen flow was started while stirring at a stirring speed of 300 rpm. After substituting with nitrogen for 30 minutes, when the internal temperature was stabilized at 80 ° C., 0.1631 parts (0.6034 mmol) of potassium peroxodisulfate dissolved in 20 parts of ion-exchanged water was added. It was. Further, a mixture of n-butyl acrylate 17.11116 parts (1333.4758 mmol), styrene 8.6094 parts (82.6633 mmol), and 5.3163 parts acrylic acid (7.44.408 mmol) was added over 1 hour. It was dropped and polymerized. 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 134 mgKOH / g. Moreover, after concentrating a refined material with an evaporator, 1 mol / L potassium hydroxide aqueous solution was added and pH was adjusted to 8, and the resin fine particle dispersion 1 was obtained. The weight average molecular weight of the copolymer constituting the resin fine particles in the obtained resin fine particle dispersion 1 was 200,000. Further, the volume cumulative median diameter of the resin fine particles in the resin fine particle dispersion 1 was 100 nm. Furthermore, the solid content concentration of the resin fine particle dispersion 1 was 10%.

( Reference Example 2)
Resin fine particle dispersion 2 was obtained in the same manner as in Example 1 except that polymer dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of polymer dispersant 2. Various physical property values of the obtained resin fine particle dispersion 2 are shown in Table 2.

( Reference Example 3)
Resin fine particle dispersion 3 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 3. Various physical property values of the obtained resin fine particle dispersion 3 are shown in Table 2.

(Example 4)
Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 4 and acrylic acid was changed to 5.3613 parts (233.1009 mmol) of 2-methacryloyloxyethyl succinate. Except for this, a resin fine particle dispersion 4 was obtained in the same manner as in Example 1 described above. Various physical property values of the obtained resin fine particle dispersion 4 are shown in Table 2.

(Example 5)
Except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 5 and acrylic acid was changed to 5.3613 parts (29.0933 mmol) of 10-undecylenic acid. In the same manner as in Example 1 described above, a resin fine particle dispersion 5 was obtained. Various physical property values of the obtained resin fine particle dispersion 5 are shown in Table 2.

(Example 6)
Except that Polymer Dispersant 1 was changed to 3.10882 parts (0.1554 mmol) of Polymer Dispersant 6 and acrylic acid was changed to 5.3613 parts (62.758 mmol) of methacrylic acid. In the same manner as in Example 1, a resin fine particle dispersion 6 was obtained. Various physical property values of the obtained resin fine particle dispersion 6 are shown in Table 2.

(Example 7)
Except that Polymer Dispersant 1 was changed to 7.10282 parts (0.1554 mmol) of Polymer Dispersant 7 and that styrene was changed to 8.6094 parts (72.8497 mmol) of vinyl toluene. Resin fine particle dispersion 7 was obtained in the same manner as Example 1. Various physical property values of the obtained resin fine particle dispersion 7 are shown in Table 2.

(Example 8)
Polymer dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of polymer dispersant 8 and n-butyl acrylate was changed to 17.1116 parts (170.9110 mmol) of methyl methacrylate. Except for the above, a resin fine particle dispersion 8 was obtained in the same manner as in Example 1 described above. Various physical property values of the obtained resin fine particle dispersion 8 are shown in Table 2.

Example 9
Resin fine particle dispersion 9 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 9. Various physical property values of the obtained resin fine particle dispersion 9 are shown in Table 2.

(Example 10)
Resin fine particle dispersion 10 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 10. Various physical property values of the obtained resin fine particle dispersion 10 are shown in Table 2.

(Example 11)
Resin fine particle dispersion 11 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 11. Various physical property values of the obtained resin fine particle dispersion 11 are shown in Table 2.

(Example 12)
Resin fine particle dispersion 12 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 12. Various physical property values of the obtained resin fine particle dispersion 12 are shown in Table 2.

(Example 13)
Resin fine particle dispersion 13 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 13. Various physical property values of the obtained resin fine particle dispersion 13 are shown in Table 2.

(Example 14)
Resin fine particle dispersion 14 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 14. Various physical property values of the obtained resin fine particle dispersion 14 are shown in Table 2.

(Example 15)
Resin fine particle dispersion 15 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 15. Various physical property values of the obtained resin fine particle dispersion 15 are shown in Table 2.

(Example 16)
Resin fine particle dispersion 16 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 16. Various physical property values of the obtained resin fine particle dispersion 16 are shown in Table 2.

(Example 17)
Resin fine particle dispersion 17 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to Polymer Dispersant 17 3.1082 (0.1554 mmol). Various physical property values of the obtained resin fine particle dispersion 17 are shown in Table 2.

(Example 18)
Resin fine particle dispersion 18 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 18. Various physical property values of the obtained resin fine particle dispersion 18 are shown in Table 2.

(Example 19)
A resin fine particle dispersion 19 was obtained in the same manner as in Example 1 except that the polymer dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of the polymer dispersant 19. Various physical property values of the obtained resin fine particle dispersion 19 are shown in Table 2.

(Example 20)
Resin fine particle dispersion 20 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 20. Various physical property values of the obtained resin fine particle dispersion 20 are shown in Table 2.

(Example 21)
Resin fine particle dispersion 21 was obtained in the same manner as in Example 1 except that the amount of potassium peroxodisulfate was changed to 2.3069 parts (8.5339 mmol). Various physical property values of the obtained resin fine particle dispersion 21 are shown in Table 2.

(Example 22)
Resin fine particle dispersion 22 was obtained in the same manner as in Example 1 except that the amount of potassium peroxodisulfate was changed to 0.0942 parts (0.3484 mmol). Various physical property values of the obtained resin fine particle dispersion 22 are shown in Table 2.

(Example 23)
Resin fine particle dispersion 23 was obtained in the same manner as in Example 1 except that the amount of potassium peroxodisulfate was changed to 3.2624 parts (12.0088 mmol). Various physical property values of the obtained resin fine particle dispersion 23 are shown in Table 2.

(Example 24)
Resin fine particle dispersion 24 was obtained in the same manner as in Example 1 except that the amount of potassium peroxodisulfate was changed to 0.0905 part (0.3347 mmol). Various physical property values of the obtained resin fine particle dispersion 24 are shown in Table 2.

(Example 25)
A resin fine particle dispersion 25 was obtained in the same manner as in Example 1 except that the stirring speed was changed to 500 rpm. Various physical property values of the obtained resin fine particle dispersion 25 are shown in Table 2.

(Example 26)
In a 300 mL four-necked flask equipped with a stirring seal, stirring rod, reflux condenser, septum rubber, nitrogen inlet tube, and thermometer, 3.1082 parts (0.1554 mmol) of polymer dispersant, acrylic acid n -17.116 parts (1333.4758 mmol) of butyl, 8.6094 parts (82.6633 mmol) of styrene, and 5.3163 parts (74.408 mmol) of acrylic acid. After mixing, 284.24 parts of ion-exchanged water was added while stirring at a stirring speed of 300 rpm, and nitrogen flow was started. After substituting with nitrogen for 30 minutes, it was placed in a heated oil bath, and when the internal temperature was stabilized at 80 ° C., 0.1631 parts (0.6034 mmol) of potassium persulfate dissolved in 20 parts of ion-exchanged water was added. 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. The obtained purified product was concentrated with an evaporator, and then a 1 mol / L aqueous potassium hydroxide solution was added to adjust the pH to 8, whereby a resin fine particle dispersion 26 was obtained. Various physical property values of the obtained resin fine particle dispersion 26 are shown in Table 2.

(Example 27)
The resin fine particle dispersion 27 was prepared in the same manner as in Example 1 except that the stirring speed was changed to 500 rpm and the amount of the polymer dispersant 1 was changed to 6.2185 parts (0.3108 mmol). Obtained. Various physical property values of the obtained resin fine particle dispersion 27 are shown in Table 2.

(Example 28)
A resin fine particle dispersion 28 was obtained in the same manner as in Example 26 except that the stirring speed was changed to 100 rpm. Various physical property values of the obtained resin fine particle dispersion 28 are shown in Table 2.

(Example 29)
The amount of n-butyl acrylate was changed to 23.0018 parts (179.4215 mmol), the amount of styrene was changed to 11.5730 parts (111.1182 mmol), and the amount of acrylic acid was 0 parts. A resin fine particle dispersion 29 was obtained in the same manner as in Example 1 except that (0 mmol) was changed. Various physical property values of the obtained resin fine particle dispersion 29 are shown in Table 2.

(Example 30)
The amount of n-butyl acrylate was changed to 11.1785 parts (87.1960 mmol), the amount of styrene was changed to 5.6243 parts (54.0018 mmol), and the amount of acrylic acid was 10. Resin fine particle dispersion 30 was obtained in the same manner as in Example 1 except that the content was changed to 7616 parts (149.3420 mmol). Various physical property values of the obtained resin fine particle dispersion 30 are shown in Table 2.

(Example 31)
The amount of n-butyl acrylate was changed to 9.7947 parts (76.41616 mmol), the amount of styrene was changed to 4.9280 parts (47.3167 mmol), and the amount of acrylic acid was 12. A resin fine particle dispersion 31 was obtained in the same manner as in Example 1 except that the content was changed to 0212 parts (166.8215 mmol). Various physical property values of the obtained resin fine particle dispersion 31 are shown in Table 2.

(Example 32)
Resin was the same as in Example 1 except that the 300 mL four-necked flask was changed to a 3 L four-necked flask and the amount of ion-exchanged water initially charged was changed to 1090.7927 parts. A fine particle dispersion 32 was obtained. Various physical property values of the obtained resin fine particle dispersion 32 are shown in Table 2.

(Example 33)
Resin fine particle dispersion 33 was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water initially charged was changed to 60.1585 parts. Various physical property values of the obtained resin fine particle dispersion 33 are shown in Table 2.

(Example 34)
Resin in the same manner as in Example 1 except that the 300 ml four-necked flask was changed to a 3 L four-necked flask and that the amount of ion-exchanged water initially charged was 1319.8248 parts. A fine particle dispersion 34 was obtained. Various physical property values of the obtained resin fine particle dispersion 34 are shown in Table 2.

(Example 35)
Resin fine particle dispersion 35 was obtained in the same manner as in Example 1 except that the amount of ion-exchanged water initially charged was changed to 56.4645 parts. Various physical property values of the obtained resin fine particle dispersion 35 are shown in Table 2.

(Example 36)
While concentrating 3388.5937 parts of resin fine particle dispersion 1, 152.12 parts of glycerin was gradually added to replace water with glycerin. Thereby, the resin fine particle dispersion 36 was obtained. Various physical property values of the obtained resin fine particle dispersion 36 are shown in Table 2. In addition, solid content concentration was computed from the mass before glycerol substitution, and the mass after glycerol substitution (calculation formula; solid content concentration [%] = solid content 10.0% before substitution x (mass after substitution [g] / Mass before substitution [g])).

(Example 37)
Resin fine particle dispersion 37 was obtained in the same manner as in Example 1 except that Polymer Dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of Polymer Dispersant 21. Various physical property values of the obtained resin fine particle dispersion 37 are shown in Table 2.

(Comparative Example 1)
A resin fine particle dispersion 38 was obtained in the same manner as in Example 1 except that the polymer dispersant 1 was changed to 3.1082 parts (0.1554 mmol) of the polymer dispersant 22. Various physical property values of the obtained resin fine particle dispersion 38 are shown in Table 2.

(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, Table 2 shows various physical property values of the obtained resin.

<Evaluation of resin fine particle dispersion>
(Adsorption to colorant)
[Preparation of sample 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. Also, 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 3. . Regarding the resin fine particle dispersion 39, since no formation of resin fine particles could be 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 (II).
Adsorption rate (%) = (1-j / k) × 100 (II)
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 3.
○: 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 (III). 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 3. 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 (III)
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 apparent from the evaluation results shown in Table 3, the adsorptivity to the colorant and the dispersion stability of the resin fine particles of Examples 1 , 4 to 37 and Reference Examples 2 and 3 were all good. On the other hand, the resin fine particles of Comparative Example 1 had poor adsorptivity to the color material. Further, Comparative Example 2 could not be evaluated because the formation of resin fine particles could not be confirmed.

<Preparation of ink>
(Example 38)
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.

( Reference Example 39)
Ink 2 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 2.

( Reference Example 40)
An ink 3 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 3.

(Example 41)
Ink 4 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 4.

(Example 42)
Ink 5 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 5.

(Example 43)
Ink 6 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 6.

(Example 44)
An ink 7 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 7.

(Example 45)
Ink 8 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 8.

(Example 46)
An ink 9 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 9.

(Example 47)
Ink 10 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 10.

(Example 48)
An ink 11 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 11.

(Example 49)
An ink 12 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 12.

(Example 50)
Ink 13 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 13.

(Example 51)
Ink 14 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 14.

(Example 52)
An ink 15 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 15.

(Example 53)
Ink 16 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 16.

(Example 54)
An ink 17 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 17.

(Example 55)
An ink 18 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 18.

(Example 56)
An ink 19 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 19.

(Example 57)
Ink 20 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 20.

(Example 58)
Ink 21 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 21.

(Example 59)
An ink 22 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 22.

(Example 60)
Ink 23 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 23.

(Example 61)
An ink 24 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 24.

(Example 62)
Ink 25 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to resin fine particle dispersion 25.

(Example 63)
An ink 26 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 26.

(Example 64)
An ink 27 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 27.

(Example 65)
An ink 28 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 28.

Example 66
An ink 29 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 29.

(Example 67)
An ink 30 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 30.

Example 68
An ink 31 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 31.

(Example 69)
Ink 32 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to 50 parts of resin fine particle dispersion 32 and the amount of ion-exchanged water was changed to 0 part.

(Example 70)
Ink 33 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to 5 parts of resin fine particle dispersion 33 and that the amount of ion-exchanged water was changed to 45 parts.

(Example 71)
Ink 34 was obtained in the same manner as in Example 38 except that resin fine particle dispersion 1 was changed to 60 parts of resin fine particle dispersion 34 and that the amount of ion-exchanged water was changed to 0 part. In addition, after adjusting pH with potassium hydroxide aqueous solution, it concentrated by the evaporator and concentration was adjusted.

(Example 72)
Ink 35 was prepared in the same manner as in Example 38, except that resin fine particle dispersion 1 was changed to 4.84 parts of resin fine particle dispersion 35 and the amount of ion-exchanged water was changed to 45.16 parts. Obtained.

(Example 73)
Except that the resin fine particle dispersion 1 was changed to 20 parts of the resin fine particle dispersion 36, the amount of glycerin was changed to 3.25 parts, and the amount of ion-exchanged water was changed to 41.75 parts. Ink 36 was obtained in the same manner as in Example 38.

(Example 74)
An ink 37 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 37.

(Example 75)
The ink 38 was changed in the same manner as in Example 38 except that the carbon black was changed to 20 parts of Pigment Blue 15: 4 (trade name “CAB-O-JET450C”, manufactured by Cabot, solid content concentration: 15%). Obtained.

(Example 76)
Ink 39 was obtained in the same manner as in Example 38, except that carbon black was changed to 20 parts of Pigment Yellow 74 (trade name “CAB-O-JET470Y”, manufactured by Cabot, solid content concentration: 15%). .

(Example 77)
Ink 40 was obtained in the same manner as in Example 38, except that carbon black was changed to 20 parts of Pigment Red 122 (trade name “CAB-O-JET465M”, manufactured by Cabot, solid content concentration: 15%). .

(Comparative Example 3)
An ink 41 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 38.

(Comparative Example 4)
An ink 42 was obtained in the same manner as in Example 38 except that the resin fine particle dispersion 1 was changed to the resin fine particle dispersion 39.

<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 4.

(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 4. 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.
A: No image rubbing and no adhesion to the Sylbon paper ○: No image rubbing but adhesion to the Sylbon paper ×: Some image rubbing −: Unable to discharge or measurement

As is clear from the results shown in Table 4, the inks of Reference Examples 39 and 40 and Examples 38 and 41 to 77 had good dispersion stability and scratch resistance after printing. On the other hand, the inks of Comparative Examples 3 and 4 had poor scratch resistance after printing and could not be used as 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 (12)

Containing an aqueous medium, and resin fine particles dispersed in the aqueous medium by a polymer dispersant,
The polymer dispersant, and structural units P derived from a benz imidazolinone derivatives represented by the following general formula (1 -1), a monomer and the following general formula represented by the following general formula (2) (3) A copolymer having a structural unit A derived from at least one of the represented monomers and a structural unit B derived from a monomer represented by the following general formula (4):
The resin fine particles are formed of a copolymer having a structural unit A derived from at least one of a monomer represented by the following general formula (2) and a monomer represented by the following general formula (3). Characteristic resin fine particle dispersion.

^{_{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 1, 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 claim 1 or 2 , wherein the polymer dispersant has a weight average molecular weight of 1,000 to 50,000. The resin fine particle dispersion according to any one of claims 1 to 3 , wherein the polymer dispersant has an acid value of 30 to 120 mgKOH / g. The resin fine particles are represented by the structural unit A derived from at least one of the monomer represented by the following general formula (2) and the monomer represented by the following general formula (3), and the following general formula (4). The resin according to any one of claims 1 to 4 , wherein the resin is formed of a copolymer having a structural unit B derived from a monomer and having a weight average molecular weight of 1,000 to 600,000. Fine particle dispersion.
^{_{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 resin fine particle dispersion according to any one of claims 1 to 5 , 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 6 , wherein the aqueous medium is water. An ink for inkjet recording comprising the resin fine particle dispersion according to any one of claims 1 to 7 , 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 8 . The inkjet recording method according to claim 9 , 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 8 . 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 the ink for ink jet recording according to claim 8 .

Images