JP6096583B2 - Method for producing resin-treated pigment composition and use thereof - Google Patents

Description

The present invention relates to a novel AB block copolymer (hereinafter also referred to as “dye block copolymer” or “dye polymer”) in which a dye skeleton is present in any one of the polymer blocks, a production method thereof, and the dye block copolymer. And a pigment dispersion containing a pigment and a dye block copolymer, useful as a novel colorant.
More specifically, the present invention provides a resin-treated pigment treated with an AB block copolymer in which a dye skeleton is present, thereby expanding the hue range, color density, color developability, transparency, etc. In addition, the resin-treated pigment composition has excellent properties required for colorants using pigments, such as dispersibility, dispersion stability, re-solubility, and alkali solubility. Relating to technology.

  In recent years, in order to provide the high color development, high transparency, and high brightness required for color filters, the pigments have been miniaturized, and the pigments have become very fine particles. Limits have been seen in its properties because it has become too fine. Accordingly, a dye having a high coloring property and a high transparency in combination with a pigment is used, and a pigment dispersion liquid using a hybrid of a dye and a pigment has been developed. On the other hand, in ink jet inks, dyes are used in combination with pigments for the purpose of expanding the color expression range.

  However, when it is used for a color filter, the dye exists as a molecule, so that the heat resistance is inferior, and the dye molecule may be volatilized by heating when forming the filter. In addition, since the colorant for oily color filters is oily, a water-soluble dye is insolubilized to form a salt and dissolve it in a solvent. In order to improve the heat resistance, a dye is introduced into a polymer skeleton and used as a hybrid of a dye and a pigment (Patent Documents 1 and 2).

  Even in an inkjet ink, when a dye is used in combination with a pigment, the dye selectively permeates into the paper and the desired color developability cannot be obtained. In particular, an aqueous inkjet uses a water-soluble dye. It is inferior in water resistance even afterwards, and may get smudged when wet with water. Therefore, a method has been adopted in which the dye is introduced into a polymer skeleton to increase water resistance or used as a dispersant (Patent Document 3).

JP 2010-174100 A JP 2011-79895 A International Publication No. 2007-089859

  However, according to the study by the present inventors, in the technique in which the dye in the conventional technique described above is introduced into the polymer skeleton and used in combination with the pigment, in addition to the problem in using the dye as it is, the dye is introduced. Since the polymer thus produced serves only as a colorant, there are cases where the amount of dye introduced is limited and there is a problem with color development, or there is a problem with the solubility of the polymer into which the dye is introduced. It was. In addition, a pigment dispersion using a polymer into which a dye is introduced has a problem that a pigment dispersant for dispersing the pigment is separately required.

  Under such circumstances, the present inventors have conducted intensive research, and as a result, developed a novel AB block copolymer and a resin-treated pigment composition that is a pigment treated with the AB block copolymer. Solved the above-mentioned problems of the prior art. This resin-treated pigment composition has been found to be a pigment that is particularly suitable for color filters and inkjets, has improved hue, improved heat resistance, can be dispersed in a medium as it is, and has excellent dispersibility. The present invention has been achieved.

That is, the present invention provides the following inventions. First, the following novel AB block copolymer is provided.
(1) 90% by mass or more is an AB block copolymer composed of a methacrylate monomer, and the polymer block of A comprises at least a methacrylate having a carboxy group as a constituent component (provided that an amino group or The polymer block of B is a quaternary ammonium nitrogen cation counterion represented by the following general formula (1), which is composed of methacrylate as a structural unit, except for the case where it contains a methacrylate having a quaternary ammonium base). And an AB block copolymer having an ion-binding moiety composed of a dye to which one or more sulfonate ions are bonded.
[X in the formula represents an organic group, and R1 to R3 each independently represents one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. D in the formula represents an organic dye molecule. ]

The following are mentioned as a preferable form of said AB block copolymer.
(2) The portion represented by the general formula (1) is contained in the AB block copolymer in the range of 5 to 40% by mass, and in the polymer block of B in the range of 20 to 80% by mass. The AB block copolymer as described above.

(3) The A-C block in which the polymer block of B is composed of the polymer block of A and a polymer block of C having a quaternary ammonium salt methacrylate represented by the following general formula (2) as a constituent component Dehydrohalogenating a copolymer and an organic dye having at least one structural portion selected from the group consisting of sulfonic acid, alkali metal sulfonate, ammonium sulfonate, and amine sulfonate in the molecule Or any of the above AB block copolymers obtained by reacting any one of a dehalogenated alkali metal salt, a dehalogenated ammonium salt or a dehalogenated amine salt.
[X in the formula represents an organic group, and R1 to R3 each independently represents one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. Y ⁻ represents a halogen ion. ]

(4) The polymer block of A has a polystyrene-equivalent number average molecular weight of 3,000 to 20,000 in the gel permeation chromatography, and a dispersity indicating the molecular weight distribution (weight average molecular weight / number average molecular weight). Is any AB block copolymer having an acid value of 30 to 250 mgKOH / g.

(5) The AB block copolymer as described above, which is obtained by utilizing living radical polymerization using a polymerization initiating compound.
(6) In the living radical polymerization, the amount of the polymerization initiating compound used is AB as described in (5) above, wherein the total number of moles of monomers forming B is 10 to 150 mol with respect to 1 mol of the polymerization initiating compound. Block copolymer.

The present invention, as another embodiment,
(7) A method for producing an AB block copolymer according to any one of the above, comprising a step of living radical polymerization in the presence of at least a polymerization initiating compound and a catalyst, and the polymerization initiating compound used in the step Is at least one of iodine and iodine compound, and the catalyst used in the step is phosphorus halide, phosphite compound, phosphinate compound, imide compound, phenol compound, diphenylmethane compound and cyclopentadiene compound There is provided a method for producing an AB block copolymer, which is at least one compound selected from the group consisting of compounds and has a polymerization temperature of 30 to 50 ° C.

The present invention, as another embodiment,
(8) Provided is a resin-treated pigment composition characterized in that the AB block copolymer described above is contained within a range of 10 to 200 parts with respect to 100 parts of pigment.

Furthermore, this invention provides the following invention regarding the manufacturing method of the said resin treatment pigment composition as another embodiment.
(9) A method for producing the above-mentioned resin-treated pigment composition, which comprises a sulfonic acid, an alkali metal sulfonate, an ammonium sulfonate, and an amine sulfonate in the molecule in an aqueous medium in the presence of the pigment. An organic dye having at least one structural portion selected from the group consisting of: and a methacrylate having at least a carboxy group as constituent components (however, including a methacrylate having an amino group or a quaternary ammonium base as a constituent component) Dehydrohalogenated AC block copolymer comprising polymer block A) and C polymer block comprising quaternary ammonium salt methacrylate represented by the following general formula (2) as a constituent component Or a dehalogenated alkali metal salt or dehalogenated ammonium salt or dehalogenated A pair of quaternary ammonium nitrogen cations represented by the following general formula (1), which is formed by reacting any of the amine salts, and comprising the polymer block of A and methacrylate as a structural unit of the pigment. A pigment treated with an AB block copolymer composed of a polymer block of B having an ion-binding portion composed of a dye having one or more sulfonate ions bound thereto as an ion A method for producing a resin-treated pigment composition.
[X in Formulas (1) and (2) represents an organic group, and R1 to R3 each independently represents any one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. D in the formula (1) represents an organic dye molecule, and Y ⁻ in the formula (2) represents a halogen ion. ]

Furthermore, the following invention is provided as the preferable embodiment.
(10) The organic dye and the AC block copolymer are reacted in an aqueous solvent having a pigment dispersed with a surfactant having a sulfonic acid group, and then treated with an AB block copolymer. A method for producing the above-mentioned resin-treated pigment composition to be a pigment.

The present invention provides each of the following inventions as another embodiment.
(11) A pigment dispersion comprising at least a pigment and any one of the AB block copolymers described above.
(12) A pigment dispersion obtained by dispersing the resin-treated pigment composition obtained by any one of the above-described methods for producing a resin-treated pigment composition.
(13) The pigment dispersion described in (11) or (12) above is dispersed in at least one dispersion medium selected from the group consisting of water, an organic solvent, and a polymerizable monomer. Pigment dispersion.

  According to the present invention as described above, the resin-treated pigment composition (colorant) obtained by using the pigment treated with the novel AB block copolymer provided by the present invention has dye coloring properties. Pigments and pigment dispersions can be used, and when used as an aqueous colorant, particularly as a colorant for inkjet inks, expansion of the hue range, improvement in transparency and gloss can be expected, and oily colorants, particularly When used as a colorant for color filters, high contrast, high transparency, and high heat resistance can be expected. In addition, the pigment treated with the AB block copolymer of the present invention not only improves the performance as the above-mentioned color, but also the polymer block of A is compatible with and dissolved in the dispersion medium, resulting in steric repulsion. Since the dispersibility of the pigment is improved and the polymer block of B is adsorbed to the pigment remarkably, the AB block copolymer as the dispersant is not detached from the pigment, so that the dispersibility and stability of the pigment Is improved.

  Further, the resin-treated pigment composition (hereinafter also referred to as resin-treated pigment) provided in the present invention can be easily finely dispersed into fine particles only by adding to and dispersing in a dispersion medium. When used in water-based inkjet inks, the polymer of A has many carboxy groups and is neutralized with water to make it water-soluble. The redispersibility which can be easily dispersed in the liquid medium can be provided. In addition, the AB block copolymer of the present invention is such that the AB block copolymer is in water, while the A polymer block is dissolved in water, but the B polymer block is not soluble in water. Therefore, there is no polymer dissolved in the liquid medium, that is, no polymer is dissolved in the liquid medium, so that the viscosity does not change and the discharge stability is useful.

  In addition, when the resin-treated pigment treated with the AB block copolymer provided in the present invention is used as a colorant for a color filter, the polymer block of A has a carbophysi group. It is easily dissolved in an alkali aqueous solution and is useful for shortening development time and sharpening pixels.

IR chart of AB block copolymer obtained from AC block copolymer-1 and Acid Red-289 of Example 1 IR chart of the AB block copolymer obtained from the AC block copolymer-2 and Direct Blue-86 in Example 4. IR chart of AB block copolymer obtained from AC block copolymer-3 and direct yellow 142 in Example 5 Filter paper spot when the treated blue pigment-1 of Example 6 was obtained Coating film spectra of Application Examples 6 and 7 and Comparative Application Example 3 Spectral data of heat resistance test of application example 6 Spectral data of heat resistance test of application example 7 Heat resistance test spectrum data of Comparative Application Example 3 Filter paper spot when the treated cyan pigment-1 of Example 11 was obtained Filter paper spot when the treated magenta pigment-1 of Example 12 was obtained

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments for carrying out the present invention.
The dye block copolymer of the present invention has a carboxy group in one polymer block (hereinafter referred to as A polymer block), and an organic dye skeleton is present in the other polymer block by ionic bonding (hereinafter referred to as B). It is an AB block copolymer characterized by having a structure (referred to as a polymer block). Since it has the above structure, the polymer block A has a property compatible with the dispersion medium, and the polymer block B has a dye skeleton and develops color. When the pigment is treated with the dye block copolymer of the present invention having such a structure, the polymer block of B acts to adsorb, coat, deposit, and encapsulate the pigment. The polymer block dissolves and dissolves in the dispersion medium, and the B polymer block acts to adsorb on the pigment, whereby the pigment can be easily dispersed, and the dispersibility and storage stability are high.

  Further, when the pigment is treated with the dye block copolymer of the present invention, the organic dye skeleton present in the polymer block of B serves to adsorb to the pigment remarkably, and functions to enhance the above-described dispersibility and storage stability. Furthermore, it becomes a novel colorant that combines the color developability of the pigment constituting the pigment block copolymer with the color developability of only the pigment. That is, by adding the hue of the pigment and the hue of the pigment, the hue range is widened in the inkjet ink, and the colorant for the color filter is improved in transparency and contrast, and has an ionic component, so that the heat resistance is also improved. be able to.

  Further, the dye block copolymer of the present invention is an AC block having an existing conventionally known dye having a sulfonic acid group, a polymer block of A having a carboxy group, and a polymer block of C having a quaternary ammonium salt. By simply mixing the copolymer, the AB block copolymer of the present invention having a structure in which the dye is ion-bonded to the B polymer block can be easily obtained by desalting and ion exchange.

  As described above, in the production of the dye block copolymer of the present invention, since an existing conventionally known dye having a sulfonic acid group can be used, in order to obtain the AB block copolymer of the present invention, a functional group is specially added to the dye. It is not necessary to introduce or design and develop a dye molecule having a new structure, which is also a very important feature for industrial production.

  In addition, the pigment treated with the dye block copolymer of the present invention has a carboxy group in the polymer block of A. Therefore, the polymer block of A is dissolved in water by neutralizing the carboxy group with an alkali. The pigment can be dispersed in water. In addition, in this case, since the polymer block of A is neutralized with an alkali, for example, when the colorant for inkjet is used, the neutralized polymer block of A exhibits water solubility. Even if the head is dried, it can be easily redispersed with an aqueous liquid medium to prevent clogging of the head.

  In addition, the polymer block of A has a carboxy group and dissolves in an organic solvent, so it can be used as an oily colorant. For example, when used as a color filter colorant as an oily colorant. As described above, good dispersibility and storage stability are exhibited. In addition to this, in the alkali development at the time of manufacturing the color filter, the polymer block A constituting the present invention is neutralized and dissolved in water, so that the alkali developability is good, the development time is shortened, and the pixel sharpness is improved. Edge can be obtained.

  In addition, since the pigment block copolymer of the present invention is a polymer having a pigment skeleton that is partly present by ionic bonds, the pigment block copolymer does not scatter like a dye, and the pigment does not volatilize by heat. There is no bleed-out where the dye appears on the surface of the film.

  Living radical polymerization is suitable as a method for obtaining the AB block copolymer of the present invention or the AC block copolymer as an intermediate thereof. There are various methods for the living radical polymerization as described below. For the following reasons, it is preferable to use living radical polymerization using a polymerization initiating compound described later. For example, there are an NMP method using nitroxide, an atom transfer radical polymerization method using a metal complex such as copper or ruthenium and a halide, and a reversible addition-fragmentation chain transfer polymerization using a sulfur compound such as dithiocarbamate. But each has its own problems. Specifically, the NMP method requires a high temperature, and the polymerization of methacrylate monomers cannot be performed satisfactorily. Atom transfer radical polymerization uses the metal complex, and the metal complex uses an amine compound as a ligand. Therefore, reversible addition-fragmentation chain transfer polymerization, which cannot polymerize a monomer having a carboxyl group as it is, has a problem that it has an odor because it uses a sulfur compound.

  Therefore, in the conventional method for producing a block copolymer used in the present invention, an iodine compound is used as a polymerization initiating compound in conventional radical polymerization, and an organic compound having active phosphorus, nitrogen, oxygen, and carbon atoms as a catalyst as necessary. Living radical polymerization using compounds is applied. As a result, a molecular weight distribution (hereinafter sometimes referred to as PDI) is easily narrow, and a block copolymer that cannot be obtained by conventional radical polymerization can be obtained. That is, a block copolymer having a uniform molecular weight can be obtained. For this reason, since a narrow molecular weight distribution and a structure called a block can be formed, the obtained block copolymer is not mixed with polymer molecules that are easily dissolved in a liquid medium or polymer molecules that are difficult to dissolve in a liquid medium, and the properties are uniform. In addition, since it can be clearly separated into a structure of a polymer block having a carboxy group and a polymer block having a dye skeleton, it is optimal for production of a block copolymer used in the present invention. Hereinafter, the constitution of the dye block copolymer of the present invention will be described in detail.

[AB block copolymer]
The AB block copolymer of the present invention is composed of 90% by mass or more of a methacrylate monomer, and the polymer block of A comprises a methacrylate having at least a carboxy group as a constituent component (however, an amino group as a constituent component). Or a quaternary ammonium nitrogen cation pair represented by the following general formula (1), in which the polymer block of B is composed of methacrylate as a structural unit. It is characterized by having an ion binding part (hereinafter referred to as “dye-containing methacrylate” or “dye monomer unit” in some cases) composed of a dye to which one or more sulfonate ions are bound as ions. To do.

[X in the formula represents an organic group, and R1 to R3 each independently represents one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. D in the formula represents an organic dye molecule. ]

  The AB block copolymer of the present invention needs to contain 90% by mass or more of a structural unit derived from a methacrylate monomer, preferably 95% by mass or more, and more preferably 100% by mass. As will be described later, in the preferred production method (polymerization method) of the AB block copolymer of the present invention, it is particularly preferable to use a methacrylate monomer as the monomer. In contrast, in the production method described later, when vinyl monomers such as styrene, acrylate monomers, and vinyl ether monomers are used, iodine bonded to the polymerization terminal is over-stabilized and added to the dissociation. This is not preferable because there is a possibility that inconveniences such as needing to be heated or not dissociating may occur. For this reason, when a large amount of monomers other than methacrylate monomers are used, there is a possibility that problems such as not having the target specific structure in the present invention or widening the molecular weight distribution may occur. However, even if it is monomers other than a methacrylate monomer, you may use it in the range which does not impair the objective of this invention as needed.

[A polymer block]
As the methacrylate monomer that is a constituent component, the polymer block of A may be a methacrylate having at least a carboxy group, and includes structural units derived from a methacrylate monomer having a carboxy group, as listed below. The polymer block of A into which a carboxy group has been introduced is ionized by being neutralized with an alkali and dissolved in water. For this reason, the AB block copolymer of the present invention can be suitably used in alkali development in the production process of a color filter. In an aqueous dispersion, the polymer block of A can be dissolved in water to take a dispersed state. It will be possible.

  Specific examples of the carboxy group-containing methacrylate monomer that can be suitably used for forming the polymer block of A include the following. For example, methacrylic acid; hydroxyl group-containing methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; dibasic acids such as phthalic acid, cyclohexanedicarboxylic acid, maleic acid, succinic acid, their acid anhydrides, and acid chlorides Half-ester type methacrylate of polycarboxy compounds such as dibasic acid and trimellitic acid obtained by reacting epoxide; Epoxy ester type methacrylate obtained by reacting glycidyl methacrylate with dibasic acid as described above; or one glycidyl group of glycidyl methacrylate An epoxy ester methacrylate obtained by reacting a dibasic acid with a hydroxyl group obtained by reacting a compound having a carboxyl group such as acetic acid or lauric acid can be used. Furthermore, in the process of making the AB block copolymer, the polymer block of A is not made a carboxy group as a constituent component, and a glycidyl methacrylate is polymerized at least as a constituent component to obtain a block copolymer. A compound having, for example, the above-mentioned dibasic acid having two or more carboxy groups in the glycidyl group by reacting the dibasic acid with a hydroxyl group obtained by reacting acetic acid, acrylic acid or methacrylic acid A carboxy group can be produced by reaction to form an AB block copolymer composed of the same polymer block A as that formed with the carboxy group-containing methacrylate listed above. include.

  As other monomer components used for forming the polymer block of A, conventionally known monomers can be used, and are not particularly limited. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-methylpropane methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate. , Isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, behenyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl methacrylate, trimethylcyclohexyl methacrylate, cyclodecyl methacrylate (Cyclo) alkyl methacrylates such as cyclodecylmethyl methacrylate, tricyclodecyl methacrylate, and benzyl methacrylate; aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate; alkenyl methacrylates such as allyl methacrylate; (poly) ethylene glycol monomethyl ether methacrylate, (poly) Glycol monoalkyl ether methacrylates such as ethylene glycol monoethyl ether methacrylate, (poly) ethylene glycol monolauryl ether methacrylate, (poly) propylene glycol monomethyl ether methacrylate;

  (Meth) acryloyloxyethyl isocyanate, isocyanate group containing 2- (2-isocyanatoethoxy) ethyl methacrylate with isocyanate group blocked with ε-caprolactone, MEK oxime, pyrazole, etc .; cyclic such as tetrahydrofurfuryl methacrylate, etc. Methacrylate; Halogen-containing methacrylates such as octafluorooctyl methacrylate and tetrafluoroethyl methacrylate; 2- (4-Benzoxy-3-hydroxyphenoxy) ethyl methacrylate, 2- (2′-hydroxy-5-methacryloyloxyethylphenyl)- 2H-benzotriazole and other UV-absorbing methacrylates; silicon atom-containing methacrylates with trimethoxysilyl groups and dimethylsilicone chains Or the like can be mentioned the door. Moreover, the macromonomer etc. which are obtained by introduce | transducing a (meth) acryl group into the one terminal of the oligomer obtained by superposing | polymerizing these monomers can be used.

  However, methacrylate having an amino group or a quaternary ammonium base must not be used for the methacrylate monomer forming the polymer block A constituting the dye block copolymer of the present invention. In the present invention, the methacrylate having an amino group or a quaternary ammonium base is introduced only into the constituent component of the polymer block of B. The reason is that when a methacrylate having an amino group or a quaternary ammonium base is used as a constituent of the polymer block of A, both the polymer block of A and the polymer block of B are adsorbed to the pigment at the time of pigment dispersion. This is because the pigment cannot be stably dispersed.

  The acid value of the polymer block A in the AB block copolymer of the present invention is preferably 30 to 250 mgKOH / g. Furthermore, it is more preferable that it is 50-200 mgKOH / g. When the acid value of the polymer block of A is within the above-mentioned numerical range, for example, it can be used as a component suitable for alkali development in the production process of a color filter, and it is neutralized with an alkali and dissolved in water and dispersed. can do. On the other hand, if the acid value of the polymer block of A is less than 30 mgKOH / g, it is not preferable because it does not dissolve or the dissolution rate becomes slow even when neutralized with alkali. On the other hand, when the acid value of the polymer block of A exceeds 250 mgKOH / g, the hydrophilicity of the exposed and hardened portion is improved in alkali development, resulting in a decrease in water resistance, and the formed pixels are random. This is not preferable because the water resistance may be inferior.

  The polymer block of A of the AB block copolymer of the present invention has a polystyrene-reduced number average molecular weight (hereinafter sometimes referred to as Mn) in a gel permeation chromatography of 3,000 to 20,000. preferable. More preferably, it is 4,000 to 15,000. If the number average molecular weight of the polymer block of A is less than 3,000, the steric repulsion of the polymer block of A does not act and there is a risk of lack of stability, and since it is a solvent-soluble polymer block, If it is too small, the solubility and compatibility may be poor, which is not preferable. On the other hand, when the number average molecular weight of the polymer block of A exceeds 20,000, the portion that dissolves or is compatible with the dispersion medium increases, so that the viscosity may increase excessively or the developability may decrease. Therefore, it is not preferable.

  The molecular weight distribution of the polymer block A of the AB block copolymer of the present invention (PDI = weight average molecular weight / number average molecular weight, hereinafter sometimes referred to as PDI) is preferably 1.5 or less. More preferably, it is 4 or less. According to the method for producing an AB block copolymer of the present invention, which will be described later, an AB block copolymer having a narrow molecular weight distribution as described above can be appropriately produced according to the design. If the PDI of the polymer block of A exceeds 1.5, the number average molecular weight is less than 3,000, and many components exceeding 20,000 are included. This is not preferable because the developability with respect to development may decrease or the viscosity may increase excessively. In the present invention, the number average molecular weight (Mn) and molecular weight distribution (PDI) were measured by GPC (Gel Permeation Chromatography) using polystyrene as a standard substance. The above is the constitution of the polymer block A of the AB block copolymer of the present invention.

[B polymer block]
Next, the polymer block B will be described. The polymer block of B is composed of methacrylate as a structural unit, and is represented by the following general formula (1). The ionic bond is composed of a dye having a sulfonate ion bound as a counter ion of a quaternary ammonium nitrogen cation. It has a configuration including at least a portion represented by the following general formula (1).
[X in the formula represents an organic group, and R1 to R3 each independently represents one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. D in the formula represents an organic dye molecule. ]

  X in the general formula (1) is an arbitrary organic group, for example, a divalent alkylene group having 1 to 18 carbon atoms, an alkenylene group or an alkynylene group, or a hydroxyl group, an ester group, a urethane group or an ether group. Are an alkylene group, an alkenylene group, an organic group having at least one introduced into the alkynylene group, or an organic group having a polyalkylene (2 to 6 carbon atoms) glycol chain, and is not particularly limited. R1, R2, and R3 in the general formula (1) may be the same or different, and are a C1-C18 alkyl group or a benzyl group, and are hydrocarbon substituents constituting a quaternary ammonium salt. is there.

  D in the general formula (1) is an organic dye molecule, which is a dye to which one or more sulfonate ions, which are counter ions of the quaternary ammonium nitrogen cation, are bonded. That is, the present invention is characterized in that the dye molecule has a structure existing in the polymer block of B by an ionic bond. Examples of D include conventionally known acidic dyes having a sulfonic acid group, but are not particularly limited, and have a xanthene structure such as Acid Red 52, Acid Red 92, Acid Red 289, and Acid Yellow 73. And those having a pyranine derivative such as Solvent Green 7 and those having a coumarin derivative such as Acid Yellow 184 can be used. Other than these, oxazole derivatives, thiazole derivatives, imidazole derivatives, imidazolone derivatives, pyrazolone derivatives, benzidine derivatives, phthalocyanine derivatives, quinacridone derivatives, diketopyrrolopyrrole derivatives, azo dyes, disazo dyes and diaminostilbene disulfonic acid Examples thereof include dyes having a sulfonic acid having various color index numbers, and dyes having a sulfonic acid group developed for inkjet.

  As described above, the polymer block B constituting the present invention is formed of methacrylate and has a structure in which organic dye molecules D are present in the structure by ionic bonds. The content of the moiety (dye monomer unit) represented by the general formula (1) of the polymer block of B is contained in the AB block copolymer of the present invention in a range of at least 5 to 40% by mass, and , B is preferably contained in the polymer block in a range of 20 to 80% by mass. That is, when the content of the dye monomer unit in the AB block copolymer is less than 5% by mass in the AB block copolymer, the coloring property of the dye and the adsorptivity with the pigment are hardly exhibited, and 40% by mass. If it exceeds 50%, the properties of the dye are strong, and in some cases, the dye cannot be dissolved in the liquid medium, which is not preferable. More preferably, it is 10-30 mass%. Further, if the content of the dye monomer unit in the polymer block of B is less than 20%, the adsorption with the pigment is weakened and dissolved in the dispersion medium, and the necessary adsorption action cannot be obtained. This is not preferable because the color characteristics may not be obtained. On the other hand, when it exceeds 80% by mass, in that case, there are too many portions having dye molecules, and the polymer block of B becomes very hard, resulting in generation of defects when detached from the pigment. This is not preferable because there is a possibility. The content of the dye monomer unit in the polymer block of B is more preferably 30 to 70% by mass.

  When forming the polymer block of B, other monomer components can be used if necessary, but conventionally known monomers can be used as the monomer, and are not particularly limited. Specifically, one or more of the above-mentioned methacrylates are used and used so that the content of the dye monomer unit is in the above-described range. In addition, when forming the polymer block of B which comprises this invention, it is good also considering the methacrylate containing a carboxy group as a structural component. As mentioned above, it is necessary to avoid the pigment-containing methacrylate from entering the polymer block of A. However, when forming the polymer block of B, the methacrylate having a carboxyl group to the extent that it does not exhibit solubility in water. May be introduced. The amount to be used is preferably in the range of 0 to 5% by mass in the monomer for forming the polymer block of B. For any reason, the present invention clearly requires that the dye monomer unit formed by the dye-containing methacrylate is introduced only into the polymer block B for any reason.

[Preparation of AB Block Copolymer]
The AB block copolymer of the present invention composed of the components as described above, after forming the polymer block of A, separately adjusting and adding the dye-containing methacrylate represented by the general formula (1), A polymer block may be formed, but more preferably, it is preferably produced by reacting the AC block copolymer with a dye having a sulfonic acid group after preparing the AC block copolymer as described below. . The reason for the preference is that the above-described production methods have problems such as complexity and cost due to the fact that the dye-containing methacrylate must be synthesized in advance, and after making the AC block copolymer, sulfonic acid This is because it is not necessary to go through a plurality of steps when the dye having a color is reacted.

(Preparation of AC block copolymer)
The AC block copolymer used to obtain the AB block copolymer of the present invention is a C block comprising the above-described polymer block of A and a quaternary ammonium salt methacrylate represented by the general formula (2) as constituent components. Easily obtained from the polymer block.
[X in the formula represents an organic group, and R1 to R3 each independently represents one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. Y ⁻ represents a halogen ion. ]

The methacrylate having the quaternary ammonium salt represented by the general formula (2) is conventionally known, and X and R1 to R3 in the general formula (2) are the explanations for the general formula (1). It is the same as that. Y ⁻ in the general formula (2) is a halogen ion, which is a chlorine ion, a bromine ion, or an iodine ion, and at least one of these is used.

  Examples of the above-mentioned methacrylate monomers having a quaternary ammonium base include conventionally known monomers, which are halide salts of tertiary amino groups, specifically 2-dimethylaminoethyl methacrylate, 2 -Diethylaminoethyl methacrylate, 2-dibutylaminoethyl methacrylate, 2-dicyclohexylaminoethyl methacrylate, A quaternary ammonium base-containing methacrylate in which an amino group is quaternized with a quaternary ammonia-forming material. More specifically, for example, benzyldimethylammonium chloride ethyl methacrylate, trimethylammonium chloride ethyl methacrylate and the like can be mentioned.

  In addition to the above, the introduction of C into the polymer block having a portion formed by a methacrylate having a quaternary ammonium salt forms a polymer block of A and then polymerizes the methacrylate having the quaternary ammonium base described above. The polymer block of C may be formed, or after the polymer block of A is formed, a polymer block having an amino group is prepared using a methacrylate monomer having a tertiary amino group. An amino halide may be reacted with an organic halide to form a quaternary ammonium salt, thereby obtaining the AC block copolymer of the present invention. Alternatively, after forming a polymer block of A, a methacrylate block having a halogenated alkyl group is polymerized to form a polymer block, and then an amine compound is reacted to form a quaternary ammonium salt contained in the polymer block of C. .

  Examples of the methacrylate having a halogenated alkyl group include 2-chloroethyl methacrylate, 2-bromo-propyl methacrylate, 1-chloro-2-hydroxypropyl methacrylate and the like, but are not particularly limited thereto. Examples of the amine compound include trimethylamine, triethylamine, dimethylbenzylamine, and dimethyllaurylamine, but are not particularly limited thereto. For the reaction, a conventionally known method can be used. This content is adjusted so as to be the content of the dye-binding monomer of the general formula contained in the B polymer block of the AB block copolymer.

  This A-C block copolymer cannot be generally specified by the monomer composition, but the polymer block of A is insoluble in water unless the carboxy group is neutralized, but the polymer block of C contains a quaternary ammonium salt. Therefore, when the AC block copolymer used in the present invention is added to water, the polymer block of A becomes fine particles, and the polymer of B dissolves because of its high affinity for water. Is finely dispersed and emulsified.

  Using this AC block copolymer, the moiety represented by the general formula (1) (pigment monomer unit) was introduced by salt exchange between the above-described dye having a sulfonic acid group and a quaternary ammonium salt. , AB block copolymer. The dye used in this case is as described above, and the sulfonic acid group may contain at least one, for example, sulfonic acid, sulfonic acid alkali metal salt or ammonium sulfonic acid salt, sulfonic acid amine. When a dye bonded as a salt is used and reacted with an AC block copolymer, the reaction of either a dehalogenated or dehalogenated alkali metal salt or a dehalogenated ammonium salt or a dehalogenated amine salt is obtained. Occur and salt exchange. For this reaction, a conventionally known method can be used, and there is no particular limitation. One or more solvents such as water, alcohol, glycol solvent, amide solvent, and the like that have high polarity for dissolving the dye are used. Particularly preferred is water, which is used in an amount of 50% by mass or more. Since the AC block copolymer of the present invention is dispersed and emulsified in water in the form of fine particles as described above, an aqueous solution of the AC block copolymer or a water-soluble solvent solution can be added to the aqueous dye solution and reacted. it can. Moreover, as conditions, it reacts by reaction at room temperature or heating. The concentration of the dye during the reaction is not particularly limited, but the reaction is preferably carried out at a concentration of 10% by mass or less.

  Further, the reactivity ratio between the sulfonic acid-containing dye and the quaternary ammonium salt contained in the AC block copolymer is not particularly limited. By making the number of moles of the dye larger than that of the quaternary salt, the dye surely reacts with the ammonium salt of the polymer block of B. Conversely, when the quaternary ammonium salt is excessive, the quaternary ammonium salt However, the used dye is surely reacted and introduced, and even if it is an equimolar amount, it is allowed to react, so that it becomes a polymer block of B forming the present invention. Preferably, when there is an excessive amount of dye, it is difficult to say that it is appropriate from the viewpoint of cost problems and treatment of waste liquid generated in the process. It should be 1.5 times or less. If the quaternary salt remains excessively, the polymer block of B may be dissolved in water when used for aqueous dispersion. However, there is no particular problem in the case of oil dispersion. In addition, in the present invention, a dye having one or more sulfonic acid groups is used as the dye. When two or more dyes are used, all the sulfonic acid groups and the quaternary ammonium salt of the AC block copolymer are used. There is no need to react, and it is only necessary that one sulfonic acid contained in the dye molecule reacts with the quaternary ammonium salt.

  Next, the molecular weights of the AB block copolymer and the AC block copolymer will be described. The molecular weight of the polymer block A constituting the AB block copolymer of the present invention is as described above. The preferable molecular weight of the polymer block A is the same in the AC block copolymer that is passed through to obtain the AB block copolymer. The number average molecular weight of these block copolymers as a whole is not particularly limited, but is a molecular weight obtained in the range of the content of the polymer block B described above. The number average molecular weight of the AB block copolymer of the present invention and the AC block copolymer used for obtaining the AB block copolymer cannot be accurately measured by a conventionally known GPC. The reason is that amphoteric carboxy groups, quaternary ammonium salts and dyes are used, so when GPC equipped with a column that does not adsorb carboxy groups is used, quaternary ammonium salts are adsorbed. When the measurement is performed with a column capable of measuring a quaternary ammonium salt, the polymer having a carboxy group is adsorbed and cannot be measured, and in any case, an accurate molecular weight cannot be obtained. Only the polymer block of A prior to the AB block copolymer can be measured.

  Therefore, since the molecular weight cannot be defined as described above, the following limitation is made so that the molecular weight of B can be defined. In the present invention, a living radical polymerization method is used for the production of the block copolymer. In general, the living radical polymerization uses a polymerization initiating compound having a group that is easily dissociated as a radical. For example, when this polymerization initiating compound is R—X, the living radical polymerization is represented by the following reaction formula (1) as a general formula.

  In the above R-X, X is eliminated by heat, light, or a catalyst to form an R radical, and one monomer is inserted into the R radical. For example, if it was normal radical polymerization in this state, the chain transfer was carried out as it was, the monomer was inserted, and eventually the radical died in the termination reaction, and because the radical lifetime was short, the chain transfer In this case, the polymer obtained can be from a small molecular weight to a large polymer, and the molecular weight distribution is wide. On the other hand, in the living radical polymerization, the reaction is biased to the left in the above formula, and when the monomer is inserted, X is immediately added and stabilized, so that the monomer insertion is stopped and no termination reaction occurs. Next, X is removed again by heat, light, or a catalyst, and X is desorbed to generate a radical at the terminal, a monomer is inserted, and X is bonded again to be stabilized. And since the radicals are generated in an ideologically uniform manner, the molecular weight is uniform. In addition, the polymerization initiating compound serves as a polymerization starting point, and the molecules extend from there, so that the molecular weight can be controlled by the amount of the polymerization initiating compound.

  In the present invention, this living radical polymerization is used, and a polymerization initiating compound and a methacrylate which is a radical polymerizable group constituting monomers used for polymerization are used. The polymer block of A has the molecular weight described above. Thus, the amount of methacrylate constituting the polymer block of A is adjusted. However, since the molecular weight of the polymer block of B cannot be measured as described above, the molar amount of methacrylate forming the polymer block of B is defined with respect to 1 mol of the starting compound. That is, in the present invention, the total number of moles of the monomers forming the B polymer block is 10 to 150 mol with respect to 1 mol of the polymerization initiating compound. The amount of the polymer block of B is adjusted in this range, and is adjusted together with the mass% contained in the polymer block of B of the dye-containing monomer described above. When the amount is less than 10 mol, the molecular weight of the polymer block of B becomes too small, and the affinity with the pigment cannot be exhibited. May occur and fine dispersion may not be possible. Preferably, it is 20 mol to 100 mol with respect to 1 mol of the starting compound of B. As described above, this molecular weight is the same for the AC block copolymer used for obtaining the AB block copolymer.

  The block copolymer of the present invention can be obtained by living radical polymerization, and particularly preferably, it is obtained by the following production method. This method is a method for obtaining the above-mentioned AB block copolymer or AC block copolymer, and specifically includes a step of living radical polymerization in the presence of a polymerization initiating compound and a catalyst. The polymerization initiating compound used in is at least one of iodine and iodine compound, and the catalyst used in this step is phosphorus halide, phosphite compound, phosphinate compound, imide compound, phenol compound, diphenylmethane And at least one compound selected from the group consisting of a cyclopentadiene compound and a polymerization temperature of 30 to 50 ° C.

  As described above, various methods have been invented for living radical polymerization, such as nitroxide mediated polymerization (NMP method) utilizing dissociation and bonding of amine oxide radicals, copper, ruthenium, nickel, Atom transfer radical polymerization (ATRP method), dithiocarboxylic acid ester or xanthate using heavy metals such as iron and ligands that form complexes with these heavy metals and using halogen compounds as starting compounds Reversible addition-fragmentation chain transfer (RAFT method) and MADIX method (Macromolecular Design via), using compounds as starting compounds and polymerizing using addition polymerizable monomers and radical initiators Interchange of Xanthate), organic tellurium, organic bismuth, Machine antimony, antimony halides, organic germanium, a method of using a heavy metal such as germanium halide (Degenerative transfer: DT method). These methods also use a polymerization initiating compound and can be applied to the present invention.

  However, each of the above-mentioned methods has a problem that it is difficult to say that it is optimal for obtaining the AB block copolymer of the present invention as described below. For example, in the NMP method, an amine oxide such as a tetramethylpiperidine oxide radical is used, but it is necessary to polymerize under a high temperature condition of 100 ° C. or higher. There is also a problem of not progressing.

  In addition, in the ATRP method, it is necessary to use a heavy metal, and since it is a polymerization method involving redox, it is necessary to remove oxygen, and in the method of polymerizing by forming a complex using an amine compound as a ligand, If an acidic substance is present, the formation of the complex is inhibited, so that it is difficult to polymerize the addition polymerizable monomer having an acid group as it is. Although it is necessary to polymerize the monomer which protected the acid group with the protecting group and to remove the protecting group after the polymerization, it is complicated and it is not easy to introduce the acid group into the polymer block.

  In the RAFT method and the MADIX method, first, special compounds such as a dithiocarboxylic acid ester and a xanthate compound are required. Since these are sulfur-based compounds, an unpleasant sulfur-based odor tends to remain in the obtained polymer. Sometimes it is colored. For this reason, it is necessary to remove an odor and coloring from the obtained polymer. Polymerization of methacrylate monomers may not be successful. In addition, sulfur esters such as dithiocarboxylic acid esters and xanthate compounds may be decomposed by amino groups, resulting in a polymer having a low molecular weight or a sulfur odor.

  Further, in the DT method, it is necessary to use heavy metals as in the ATRP method. For this reason, there is a problem that it is necessary to remove heavy metals from the obtained polymer and to purify waste water containing the generated heavy metals.

  Under such circumstances, the polymerization method used in the present invention does not require the use of heavy metal compounds, does not require purification of the polymer, does not require the synthesis of special compounds, and is relatively inexpensive on the market. It can be easily manufactured by using a simple material. In addition, the polymerization conditions are mild, and the polymerization can be performed under the same conditions as the conventional radical polymerization method. It should be noted that a monomer having a carboxy group or a phosphate group can be directly subjected to living radical polymerization. It is in.

  Specifically, the method for producing an AB block copolymer of the present invention includes a step of living radical polymerization of a monomer component containing a methacrylate monomer (polymerization step) in the presence of a polymerization initiating compound and a catalyst. And The polymerization initiating compound is at least one of iodine and an iodine compound. In this living radical polymerization employed in the present invention, various functional groups can be used.

  In the polymerization step, at least one of iodine and an iodine compound is used as a polymerization initiating compound, and a monomer component containing a methacrylate monomer is polymerized by living radical polymerization. When heat or light is applied to iodine or iodine compound used as a polymerization initiating compound, iodine radicals are dissociated. Then, after the monomer is inserted in a state in which the iodine radical is dissociated, the iodine radical is immediately bonded again to the polymer terminal radical and stabilized, and the polymerization reaction proceeds while preventing the termination reaction.

  Specific examples of the iodine compound include alkyl iodides such as 2-iodo-1-phenylethane and 1-iodo-1-phenylethane; 2-cyano-2-iodopropane, 2-cyano-2-iodobutane, 1 Cyano group-containing iodides such as cyano-1-iodocyclohexane, 2-cyano-2iodo-2,4-dimethylpentane, 2-cyano-2-iodo-4-methoxy-2,4-dimethylpentane, etc. Can be mentioned.

  As these iodine compounds, commercially available products may be used as they are, but those prepared by a conventionally known method can also be used. For example, an iodine compound can be obtained by reacting an azo compound such as azobisisobutyronitrile with iodine. Further, the iodine compound can be obtained by reacting an organic halide obtained by substituting iodine of the above iodine compound with a halogen atom such as bromine or chlorine and an iodide salt such as quaternary ammonium iodide or sodium iodide, and exchanging the halogen. Can be obtained.

  In the polymerization step, a catalyst capable of extracting iodine of the polymerization initiating compound is used together with the polymerization initiating compound. Examples of catalysts include phosphorus compounds such as phosphorus halides, phosphite compounds, and phosphinate compounds; nitrogen compounds such as imide compounds; oxygen compounds such as phenol compounds; diphenylmethane compounds and cyclopentadiene compounds. It is preferable to use the following hydrocarbon compound. In addition, these catalysts can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the phosphorus compound include phosphorus triiodide, diethyl phosphite, dibutyl phosphite, ethoxyphenyl phosphinate, and phenylphenoxy phosphinate. Specific examples of the nitrogen compound include succinimide, 2,2-dimethylsuccinimide, maleimide, phthalimide, N-iodosuccinimide, and hydantoin. Specific examples of the oxygen-based compound include phenol, hydroquinone, methoxyhydroquinone, t-butylphenol, catechol, and di-t-butylhydroxytoluene. Specific examples of the hydrocarbon compound include cyclohexadiene and diphenylmethane.

  The amount of the catalyst used (number of moles) is preferably less than the amount of use of the polymerization initiating compound (number of moles). If the amount of the catalyst used (number of moles) is too large, polymerization may be over-controlled and polymerization may not proceed easily. Moreover, it is preferable that the temperature (polymerization temperature) in the case of living radical polymerization shall be 30-100 degreeC. If the polymerization temperature is too high, iodine at the polymerization terminal may be decomposed, and the terminal may not be stable, resulting in living polymerization. In this polymerization method, it is preferable that iodine is bonded to the terminal, and the iodine is dissociated as a radical to generate a radical so that the terminal is stable. Here, in the case of acrylate, vinyl, etc., the terminal is a secondary iodide, which is relatively stable and does not come off as an iodine radical, and there is a possibility that the polymerization does not proceed or the distribution becomes wide. Although dissociation can be carried out by raising the temperature, it is preferred that the polymerization be carried out gently in the above temperature range from the viewpoint of environment and energy. Therefore, a tertiary iodide which is easy to generate radicals and is relatively stable is preferable, and a methacrylate monomer is suitable for the living radical polymerization used in the present invention.

  In the polymerization step, a polymerization initiator that can generate radicals is usually added. As the polymerization initiator, conventionally known azo initiators and peroxide initiators are used. It is preferable to use a polymerization initiator that generates radicals sufficiently within the above polymerization temperature range. Specifically, an azo initiator such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) is preferably used. The amount of the polymerization initiator used is preferably 0.001 to 0.1 mol times, more preferably 0.002 to 0.05 mol times the monomer. If the amount of the polymerization initiator used is too small, the polymerization reaction may not proceed sufficiently. On the other hand, if the amount of the polymerization initiator used is too large, a normal radical polymerization reaction that is not a living radical polymerization reaction may proceed as a side reaction.

  Living radical polymerization may be bulk polymerization that does not use an organic solvent, but is preferably solution polymerization that uses an organic solvent. The organic solvent is preferably one that can dissolve components such as a polymerization initiator compound, a catalyst, a monomer component, and a polymerization initiator.

  Specific examples of organic solvents include hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene and other hydrocarbon solvents; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, benzyl alcohol Alcohol solvents such as cyclohexanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol propyl ether, diglyme, triglyme, tetra Glyme, dipropylin glycol dimethyl ether, buty Glycol solvents such as carbitol, butyltriethylene glycol, methyl dipropylene glycol, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol butyl ether acetate, diethylene glycol monobutyl ether acetate; diethyl ether, dipropyl ether, methylcyclopropyl ether Ether solvents such as tetrahydrofuran, dioxane and anisole; ketone solvents such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and acetophenone; methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, Caprolactone, methyl lactate, ethyl lactate, dimethyl oxalate, adip Ester solvents such as dimethyl acid and dimethyl glutarate; halogenated solvents such as chloroform and dichloroethane; amide solvents such as dimethylformamide, dimethylacetamide, pyrrolidone, N-methylpyrrolidone and caprolactam, as well as dimethyl sulfoxide, sulfolane and tetramethyl Examples include urea, ethylene carbonate, propylene carbonate, and dimethyl carbonate. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types.

  Moreover, the organic solvent used for these polymerization can be used as it is as a solution, and if necessary, the polymer can be taken out from the solution and solidified. This method is not particularly limited. For example, it can be precipitated as a poor solvent and filtered and dried, or the solution can be dried to take out only the polymer to obtain a solid polymer. The obtained solid polymer may be used as it is, or may be used as a polymer solution by adding a solvent.

  In the case of solution polymerization, the solid content concentration (monomer concentration) of the polymerization solution is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass. When the solid content concentration of the polymerization liquid is less than 5% by mass, the monomer concentration may be too low to complete the polymerization. On the other hand, when the solid content concentration of the polymerization liquid exceeds 80% by mass or bulk polymerization, the viscosity of the polymerization liquid becomes too high, and stirring tends to be difficult and the polymerization yield tends to decrease. Living radical polymerization is preferably carried out until the monomer runs out. Specifically, the polymerization time is preferably 0.5 to 48 hours, and more preferably 1 to 24 hours. The polymerization atmosphere is not particularly limited, and may be an atmosphere in which oxygen exists within a normal range or a nitrogen stream atmosphere. Moreover, the material (monomer etc.) used for superposition | polymerization may use what removed the impurity by distillation, activated carbon treatment, an alumina treatment, etc., and may use a commercial item as it is. Furthermore, polymerization may be performed under light shielding, or polymerization may be performed in a transparent container such as glass.

As described above, the AB block copolymer of the present invention and the AC block copolymer prepared to obtain the polymer are used in a molar ratio of the use balance of the methacrylate-based monomers and the polymerization initiating compound in the living radical polymerization. By adjusting, the molecular weight of the main chain is controlled. Specifically, a polymer whose main chain has an arbitrary molecular weight can be obtained by appropriately setting the number of moles of the monomer with respect to the number of moles of the polymerization initiating compound. For example, when 1 mol of a polymerization initiating compound is used and 500 mol of a monomer having a molecular weight of 100 is used for polymerization, a polymer having a theoretical molecular weight of “1 × 100 × 500 = 50000” can be obtained. That is, the theoretical molecular weight of the main chain polymer can be calculated by the following formula (3). The above “molecular weight” is a concept including both the number average molecular weight (Mn) and the weight average molecular weight (Mw).
“Theoretical molecular weight of main chain polymer” = “1 mol of polymerization initiation compound” × “monomer molecular weight” × “number of moles of monomer / number of moles of polymerization initiation compound” (3)
The amount of the polymerization initiating compound is as described above.

  In the polymerization step, there may be a case where a bimolecular termination or a disproportionation side reaction is involved, so that a main chain polymer having the above theoretical molecular weight may not be obtained. It is preferable that these are obtained without causing side reactions. The polymerization rate may not be 100%. Furthermore, once the polymerization is completed, the polymerization may be completed by adding a polymerization initiating compound or a catalyst and consuming the remaining monomer. That is, in the present invention, an AB block copolymer or an AC block copolymer having a specific structure is generated by the production method as described above, and this may be included as a main component. Preferably, if 80% or more of the produced copolymer is the specific block copolymer of the present invention, the effect is sufficiently obtained.

  The order of polymer polymerization for blocking the AB block copolymer of the present invention is the general order for forming the dye monomer unit described above after polymerizing a methacrylate having a carboxy group to obtain a polymer block of A. The dye-containing methacrylate of the formula (1) or the methacrylate having a quaternary ammonium salt may be polymerized to form a polymer block of B or C. Conversely, after forming the polymer block of B, a carboxy group A polymer block of A may be formed by polymerizing a methacrylate having the following formula. However, preferably, after polymerizing a methacrylate having a carboxy group to obtain a polymer block of A, the above-described dye-containing methacrylate of the general formula (1) or a methacrylate having a quaternary ammonium salt is polymerized to obtain B or It is better to form a polymer block of C. The reason for this is that after the dye-containing methacrylate or the methacrylate having a quaternary ammonium salt is polymerized first, all those monomers may be polymerized, but if these monomers remain, the polymer block of A This is because those monomers are introduced and the AB block copolymer of the present invention may not function.

  The AB block copolymer or the AC block copolymer obtained as described above may remain in a state in which iodine atoms derived from the polymerization initiating compound are bonded, but the iodine atoms may be eliminated. preferable. The method for desorbing iodine atoms from the AB block copolymer is not particularly limited as long as it is a conventionally known method. Specifically, the AB block copolymer may be heated or treated with an acid or alkali. Further, the AB block copolymer may be treated with sodium thiosulfate or the like. The detached iodine is preferably removed by treatment with an iodine adsorbent such as activated carbon or alumina.

  Since the AB block copolymer obtained as described above has the dye molecule D, it can be used as a colorant as it is, but is preferably used as a pigment dispersant. In that case, the pigment and the AB block copolymer of the present invention may be added and dispersed in a dispersion medium to form a pigment dispersion. Further, a pigment, a dye having a sulfonic acid, and the above-described AC block copolymer for obtaining an AB block copolymer are added and dispersed in a dispersion medium simultaneously with a salt exchange reaction. It can also be obtained.

  However, according to the study by the present inventors, in this case, the polymer block of B has a dye skeleton in its structure and has many ionic bonds, so it is hardly soluble in a solvent. It may be difficult to disperse the pigment in the medium using the AB block copolymer of the present invention as a dispersant. The reason is considered to be that the polymer block of B is insoluble, so that it cannot be adsorbed to the pigment and is difficult to disperse.

<Resin-treated pigment composition>
Therefore, the present invention provides a resin-treated pigment composition (hereinafter also referred to as a resin-treated pigment) in which a more preferable AB block copolymer is adsorbed on the surface of the pigment. This is a treated pigment in which the pigment is previously treated with an AB block copolymer, and the polymer block of B is hardly soluble in a solvent and has a high affinity with the pigment. Can be applied to the pigment, and the AB block copolymer can be adsorbed to the pigment more reliably than the use form as the pigment dispersant. A resin-treated pigment showing When this resin-treated pigment is dispersed in a liquid medium, the polymer block of B is adsorbed and encapsulated in the pigment, and the polymer block of A is dissolved and compatible in the liquid medium and the dispersion medium. By repulsion, the pigment can be dispersed in the fine particles, the storage stability is high, the pigments are not aggregated, the viscosity of the dispersion is not increased, etc., and a very good pigment dispersion can be obtained. Another major feature is that a finely dispersed pigment dispersion can be easily obtained simply by mixing and dispersing at least the obtained resin-treated pigment and a liquid medium as a dispersion medium. Furthermore, in addition to the color performance of the pigment, the color performance of the dye of the AB block copolymer is added, and unprecedented color performance is exhibited.

  The resin-treated pigment of the present invention having the above-described excellent performance will be described. This resin-treated pigment is characterized by comprising 10 to 200 parts of the AB block copolymer described above with respect to 100 parts of pigment. On the other hand, when the amount of the AB block copolymer is less than 10 parts, the function as a dispersing agent when dispersed is insufficient, and the pigment cannot be finely dispersed or its storage stability is poor. On the other hand, when the amount is more than 200 parts, the pigment content is relatively small, and the pigment performance may not be exhibited. More preferably, it is 30-100 parts.

  The pigment used in the above is not particularly limited, and is used for color filters and inkjet inks. RGB red, green, blue, yellow, violet pigment, YCMBk, yellow, cyan, magenta, black as complementary colors. A pigment showing a color is used.

  Specifically, pigments used in inkjet inks include Color Index Number (CI) Pigment Blue-15: 3, 15: 4, C.I. I. Pigment red-122, 269, C.I. I. Pigment violet-19, C.I. I. Pigment yellow-74, 155, 180, 183, C.I. I. Pigment green-7, 36, 58, C.I. I. Pigment orange-43, C.I. I. Pigment black-7, C.I. I. Pigment White-6. Its average primary particle size is less than 350 nm. More preferably, C.I. I. Pigment Blue-15: 3, 15: 4, C.I. I. Pigment red-122, 269, C.I. I. Pigment violet-19, C.I. I. Pigment yellow-74, 155, 180, 183, C.I. I. Pigment green-7, 36, 58, C.I. I. Pigment orange-43, C.I. I. For Pigment Black-7, the average particle size is less than 150 nm. I. About pigment white-6, less than 300 nm is good. For the clogging of the head of the ink jet recording apparatus and the sharpness of the image, it is more preferable that the particle diameter is smaller. The pigment used above may be a surface treatment agent such as a coupling agent or a surfactant, or a treated pigment that has been surface-treated or encapsulated with a resin.

  As the pigment for the color filter, an organic pigment or an inorganic pigment for black matrix is preferably used. Examples of the red pigment include color index (hereinafter, CI) pigment red (PR) 56, 58, 122, 166, 168, 176, 177, 178, 224, 242, 254, and 255. Examples of green pigments include C.I. I. Pigment Green (PG) 7, 36, 58, poly (14-16) bromo copper phthalocyanine, poly (12-15) brominated-poly (4-1) chlorinated copper phthalocyanine. Examples of blue pigments include C.I. I. Pigment blue 15: 1, 15: 3, 15: 6, 60, 80, and the like.

  Examples of complementary color pigments or multicolor pixel pigments for the color filter pigments described above include the following. Examples of yellow pigments include C.I. I. Pigment Yellow (PY) 12, 13, 14, 17, 24, 55, 60, 74, 83, 90, 93, 126, 128, 138, 139, 150, 154, 155, 180, 185, 216, 219, C . I. CI pigment violet (PV) 19, 23. Examples of black pigments for black matrix include C.I. I. CI pigment black (PBK) 6, 7, 11, 26, and a copper-manganese-iron-based composite oxide. The surface of these pigments may be treated with a pigment surface modifier called a synergist, or may be treated with a surfactant or the like.

  The synergist is not particularly limited, and a dye skeleton compound having an acid such as a sulfonic acid group, a carboxyl group, a phosphoric acid group, an amino group, or an alkaline group is used. In particular, the use of a synergist having a sulfonic acid is preferable because it can be remarkably adsorbed by salt exchange with the quaternary ammonium salt of the AC block copolymer carried out by the production method of the present invention. The surfactant is not particularly limited. As described above, when a surfactant having a sulfonic acid group or a surfactant having a sulfonic acid group such as sodium dodecylbenzenesulfonate or sodium lauryl sulfate is used, the quaternary ammonium salt of the AC block copolymer It is preferable because it reacts and remarkably adsorbs.

  The number average particle diameter after dispersion of the pigment is not particularly limited, but is 10 to 200 nm, preferably 20 to 150 nm, for carbon black and organic pigments. For inorganic pigments such as titanium oxide, 50 to 300 nm, more preferably 100 to 250 nm is preferable. The average particle diameter of the pigment can be determined by observing with a transmission electron microscope (TEM). The pigment obtained by treating the pigment thus finely divided with the AB block copolymer of the present invention is useful as a colorant that gives high color developability, high image quality, high gloss, high printability, and the like.

  Hereinafter, a production method for obtaining the above-described resin-treated pigment will be described. It can be obtained by mixing the pigment and the AB block copolymer of the present invention or a solvent solution thereof. However, as described above, since the polymer block of B is hardly soluble in the liquid medium, it may be a simple mixture. There is. Therefore, it can be stably obtained by the following method.

  That is, at least one or more structural parts selected from the group consisting of one or more sulfonic acids, alkali metal sulfonates, ammonium sulfonates, and amine sulfonates in an aqueous medium in the presence of a pigment. The A-C block copolymer is reacted with either a dehalogenated or dehalogenated alkali metal salt, a dehalogenated ammonium salt or a dehalogenated amine salt to form an A-B block copolymer. The resin-treated pigment may be treated in the above manner.

  More specifically, the following procedure is used. The pigment is added to an aqueous medium or an aqueous medium to which an organic solvent that dissolves in water is added as necessary. The pigment may be a powdered pigment, but preferably, a water paste before drying the pigment is used as described below. Since the pigment is a large crystal as it is after being synthesized, it is sized, refined and pigmented to obtain pigment particles having a fine primary particle size. Then, it is dried and pulverized to obtain a pigment powder. By this drying, the primary particle pigments aggregate to form secondary particles, resulting in coarse pigment particles. For this reason, this is dispersed with a mechanical medium and finely dispersed to obtain a pigment dispersion. Therefore, when the pigment is treated with the AC block copolymer and dye used in the present invention, the pigment can be treated in a fine particle state, which is preferable.

  More specifically, it is preferable to use a water paste before drying the pigment to form a water slurry having a pigment solid content concentration of 0.5 to 30%. This slurry is peptized by a conventionally known method. The method is not particularly limited, and a disperser, a homogenizer, a dispersing machine such as a vertical bead mill, a horizontal bead mill, and a high-pressure homogenizer, if necessary, a kneader such as a kneader, flasher, two rolls, and three rolls are used. Just do it. This condition is conventionally known and is not particularly limited. At this time, the above-described pigment surface modifier and surfactant can be added as necessary. The addition of this surfactant will be described later.

  An organic dye having one or more sulfonic acids, or alkali metal sulfonates, or ammonium sulfonates, or amine sulfonates is then added to the structure characterizing the present invention and homogenized. At this time, when the dye is difficult to dissolve, it may be added after being dissolved in an organic solvent, preferably a water-soluble organic solvent. There is no limitation on this stirring and its conditions.

  Next, the above-described AC block copolymer used in the present invention is added. The AC block copolymer obtained by polymerization may be added as it is in a polymerization solvent solution, or the AC block copolymer obtained by polymerization may be taken out as a solid and added as a solid. The taken out product may be dissolved in another liquid medium and added. When the polymerization solvent is added as a solution, the polymerization solvent is preferably an organic solvent that dissolves in water, an alcohol-based solvent, a glycol-based solvent, an amide-based solvent, or the like, and more preferably an A-C block copolymer is polymerized. As the solvent for the above, it is suitable to use an alcohol-based, glycol-based, or amide-based water-soluble solvent because a process such as polymer formation is not necessary.

  The solvent used in this case is preferably an alkylene (carbon number: C2-C6) diol; an alkylene (carbon number: C3-C10) triol; a mono- or dialkyl (carbon number: C1-C4) ether; n = 2 to 5) alkylene (carbon number: C2-4) glycol mono or dialkyl (carbon number: C1 to C4) ether; mono or poly (n = 2 to 5) ethylene glycol monoalkyl ether acetate; Can be mentioned. Specifically, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-3-hydroxy-1-butanol Alkylene (carbon number: C2-C6) diol; glycerol, trimethylolpropane, alkylene (carbon number: C3-C10) triol such as 1,2,4-butanetriol; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene Mono-, dialkyl ethers of the above-mentioned alkylene (carbon number: C2-C6) diols such as glycol monomethyl ether, propylene glycol monopropyl ether, 3-methyl-3-methoxy-1-butanol; diethylene glycol monobutyl (Poly n = 2-5) alkylene (carbon number: C2-4) glycol such as ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, tripropyne glycol monomethyl ether Mono- or dialkyl (carbon number: C1-C4) ether; mono- or poly (n = 2-5) ethylene glycol glycol monoalkyl ether acetate such as diethylene glycol monoethyl ether acetate; amides such as 2-pyrrolidone and N-methylpyrrolidone A solvent can be preferably used.

  Next, when an AC block copolymer is added, a phenomenon in which thickening occurs may be observed depending on the pigment concentration. This is because the A-C block copolymer and the sulfonic acid of the dye are eliminated, becoming an A-B block copolymer, insolubilized in water, and at that time, it is adsorbed remarkably to the pigment. Therefore, it is considered that the pigment surface becomes hydrophobic and fluidity is weakened. When the slurry of the dye and pigment in this case is spotted on the filter paper, it can be confirmed that the dye is separated from the dye and the dye is bleed. However, when the AC block copolymer is added, the dye becomes insoluble and the bleed disappears. It can be seen that the pigment was treated with the AB block copolymer of the present invention. This method of adding the AC block copolymer may be added all at once or gradually. You may add at room temperature or heating. The stirring time is not particularly limited, and the conditions are arbitrary. Next, the resin-treated pigment of the present invention can be obtained by filtration, washing, drying and pulverization. When used for aqueous dispersion, it can be used in the form of a water paste without drying.

  Moreover, when using this water paste, the surfactant which has a sulfonic acid group can be used. This is a method capable of treating a pigment having a finer particle diameter, although there is no problem with a water paste as described above. Even the water paste before drying of pigments that are not secondary particles is loose secondary agglomeration due to pressure during storage, partial drying, and hydrophobicity, and coarse when treated with the same particle size There may be particles. Therefore, it is preferable to use the pigment finely dispersed in water with a surfactant having a sulfonic acid group in advance. For this dispersion, a conventionally known method is used and there is no particular limitation. However, a surfactant having a pigment concentration of 10 to 40% by mass and a sulfonic acid group is used in an amount of 1 to 10% based on the pigment. Then, using an additive such as an antifoaming agent, it is dispersed by a conventionally known dispersion method such as bead dispersion or ultrasonic dispersion. Examples of the disperser used at that time include a kneader such as a kneader, two rolls, three rolls, and Miracle KCK (Asada Steel Corporation, trade name), an ultrasonic disperser, and a microfluidizer that is a high-pressure homogenizer. (Trade name, Mizuho Industry Co., Ltd.), Nanomizer (trade name, Yoshida Kikai Kogyo Co., Ltd.), Starburst (trade name, Sugino Machine Co., Ltd.), G-Smasher (trade name, Rix Corporation), etc. . In the case of using a bead medium such as glass or zircon, a ball mill, a sand mill, a horizontal media mill disperser, a colloid mill, or the like can be used. The dispersion formulation is not particularly limited. If necessary, it is also a preferable form to use other additives to such an extent that the quality is not affected. The additive used in this case is not particularly limited. For example, an antifoaming agent, a leveling agent, a light stabilizer, a UV absorber, a surface conditioner, a coloring agent such as a dye, an improvement in film properties and adhesiveness. One or more kinds of various additives such as a polymer component, a water repellent agent, an oil repellent agent, a crosslinking agent with a chemical bond, a matting agent, a silane coupling agent, and a surfactant for improvement can be arbitrarily added.

  Using the pigment dispersion dispersed with the surfactant having a sulfonic acid group, as described above, a dye having a sulfonic acid is added, mixed, stirred, and dispersed as necessary. A block copolymer can be added to obtain a resin-treated pigment. Since the treatment is performed in a state of being dispersed in the fine particles, a resin-treated pigment in which the fine pigment is treated can be obtained.

  The pigment dispersion of the present invention comprises at least the pigment and the AB block copolymer of the present invention, and more preferably, the resin treatment of the pigment obtained as described above and the AB block copolymer. It is preferable to disperse using a pigment. A pigment dispersant can be added separately as necessary. However, when the resin-treated pigment obtained as described above is used, basically no pigment dispersant is required. When the resin-treated pigment of the present invention is used, the AB block copolymer acts as a pigment dispersant, that is, the polymer block of B is adsorbed to the pigment and is not soluble in the liquid medium, so it does not leave the pigment. This is because it can be dissolved in a dispersion medium to be in a dispersed state.

  As the dispersion medium used at this time, a liquid medium or a solid medium can be used, but a liquid medium is preferable. Specific examples of the liquid medium include water, the above-described organic solvent, UV ink, polymerized toner, and the like. The polymerizable monomer used is mentioned. That is, the pigment dispersion of the present invention is characterized in that it can be used as both an aqueous colorant and an oily colorant.

  The polymerizable monomer used above will be described. For example, the above-mentioned methacrylates; acrylic acid monomers and oligomers are suitable. Specific examples of monomers include butyl acrylate, 2-methylpropane acrylate, t-butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, isodecyl acrylate, lauryl acrylate, tetradecyl Acrylate, octadecyl acrylate, behenyl acrylate, isostearyl acrylate, cyclohexyl acrylate, t-butylcyclohexyl acrylate, isobornyl acrylate, trimethylcyclohexyl acrylate, cyclodecyl acrylate, cyclodecylmethyl acrylate, tricyclodecyl acrylate, benzyl acrylate, phenoxy Ethyl acrylate, phenyl Acrylate, naphthyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, (poly) ethylene glycol monomethyl ether acrylate, (poly) ethylene glycol monolauryl ether acrylate, (poly) propylene glycol monomethyl ether acrylate, Examples include octafluorooctyl acrylate, tetrafluoroethyl acrylate, acrylate of ethylene oxide adduct of nonylphenol, acryloyloxyethyl phosphate, acryloyloxyphthalic acid, and the like. The above-mentioned methacrylate monomers can also be used. In addition, vinyl monomers such as styrene can be used.

  The radical polymerizable oligomer is a compound having two or more polymerizable groups in one molecule, and specific examples thereof include ethylene glycol, butanediol, hexanediol, nonanediol, cyclohexanedimethanol, butenediol. , Diacrylic acid ester of alkyl, alkenyl, cycloalkyl diol such as butynediol neopentyl glycol; poly (n = 2 or more) glycol ethers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide adduct of bisphenol A Diacrylates of poly (hexanediol adipate), polybutanediolsuccinic acid, polyacrylates of polyester diols such as polycaprolactone; Diacrylate of carbonate diol such as len carbonate; Polyacrylate of urethane polyol obtained by diisocyanate such as toluene diisocyanate and diol, triol, diamine, etc .; Polyacrylate of epoxy resin such as adduct of bisphenol A glycidyl ether; Polyglycerin , Trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol and other polyhydric hydroxyl group-containing compounds, and polyacrylates of these alkylene oxide adducts.

  As a cationically polymerizable compound, although it can contribute also as above-mentioned acrylate and radical polymerizability, a vinyl ether type can be used. Specific examples of vinyl ethers include monofunctional vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, and hydroxyethyl vinyl ether; (poly) ethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, trimethylolpropane trivinyl ether, etc. Can be used. Furthermore, epoxy compounds and oxetane compounds can also be used.

  The dispersion medium may be a solid medium as described above, and can be applied to a thermoplastic resin or a thermosetting resin. Thus, the pigment dispersion of the present invention is also used for coloring plastic moldings, films, toners and the like.

  In particular, when the oily dispersion is exemplified as the dispersion of the liquid medium, a color filter colorant may be mentioned. As its use, specifically, the resin-treated pigment obtained as described above is blended in an organic solvent so that the pigment content is 5 to 40% by mass, and if necessary, alkali development A binder that imparts properties is added and dispersed by the dispersion method described above to obtain a colorant.

  As described above, the pigment is used as the pigment, but the following is preferable. It is preferable that the average particle diameter is 10 to 150 nm, and it is more preferable to use a pigment having an average particle diameter of 20 to 80 nm. In particular, when the resin-treated pigment of the present invention is used as a colorant for a color filter, it is preferable to use a pigment having a primary average particle size of 10 to 50 nm for the constitution. Thus, the pigment dispersion of the present invention obtained by dispersing the finely divided pigment is particularly suitable as a colorant capable of producing a color filter having high transparency and high contrast. When the average particle diameter is less than 10 nm, the pigment becomes primary particles or less, and various physical properties such as light resistance and heat resistance may be deteriorated. On the other hand, when it exceeds 150 nm, transparency and contrast may be deteriorated. The average particle diameter of the pigment can be determined by observing with a transmission electron microscope (TEM). The resin-treated pigment of the present invention contains a pigment dispersant that can stably and highly finely disperse the finely divided pigment. For this reason, the pigment dispersion of the present invention using the resin-treated pigment of the present invention is such that the above extremely fine pigment is dispersed in a good state and has excellent long-term storage stability. .

  If necessary, a dye derivative can be added in the dispersion step of the pigment dispersion of the present invention. Examples thereof include dye derivatives having an acidic functional group and a basic functional group, and the same or similar skeleton as the pigment and the same or similar skeleton as the compound used as the raw material of the pigment are preferable. Specific examples of the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton.

  Since the resin-treated pigment of the present invention has a carboxyl group in the polymer block A, it is characterized in that it can be alkali-developed as it is. If necessary, an alkali-developable polymer can be added to the resin-treated pigment. This alkali-developable polymer has an acid group such as a carboxyl group in its structure, and the acid group is neutralized with an aqueous alkali solution so that it is soluble in water and can be developed.

  As the alkali-developable polymer, a photosensitive resin having a photosensitive group such as an unsaturated bond group or a non-photosensitive resin can be used. Specific examples of the photosensitive resin include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polyacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, an unsaturated polyester resin, and a polyester. Examples thereof include acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins. Specific examples of the non-photosensitive resin include cellulose acetate resin, nitrocellulose resin, styrene (co) polymer, polyvinyl butyral resin, aminoalkyd resin, polyester resin, amino resin-modified polyester resin, polyurethane Resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, hydroxyethyl cellulose, styrene-maleic acid ester copolymer, (meth) acrylic acid ester Examples thereof include system (co) polymers. These alkali-developable polymers can be used singly or in combination of two or more. In addition, it is preferable that it is 5-300 mass parts with respect to 100 mass parts of pigments, and, as for content of the alkali developable binder in a resin-treated pigment, it is more preferable that it is 10-100 mass parts.

  Moreover, it is also a preferable aspect that the resin-treated pigment of the present invention further contains an unsaturated bond group-containing block copolymer obtained by reacting a (meth) acrylate having a glycidyl group or an isocyanate group. This unsaturated bond group-containing block copolymer is a component that can be photocured to form a film. For this reason, the intensity | strength (resistance) of the pixel of a color filter can be improved. Further, the edge of the pixel can be formed sharply, and the solvent resistance of the formed pixel can be improved. The unsaturated bond group in the unsaturated bond group-containing block copolymer is preferably an acryl group or a methacryl group. These unsaturated bond groups are introduced into the unsaturated bond group-containing block copolymer by a conventionally known method.

  The above-mentioned organic solvent can be used for the liquid medium which comprises the pigment dispersion of this invention which is an oil-based pigment dispersion liquid, and can be used individually by 1 type or in combination of 2 or more types. Particularly preferred are glycol ester solvents such as propylene glycol monomethyl ether acetate.

  A conventionally known additive may be further added to the pigment dispersion of the present invention. Specific examples of the additive include an ultraviolet absorber, a leveling agent, an antifoaming agent, and a photopolymerization initiator. Moreover, you may add the monomer which has unsaturated bonds, such as a methacrylate and an acrylate, as a reactive diluent.

  In producing the pigment dispersion of the present invention, each component may be blended at a time, or may be blended individually. A resin-treated pigment and components such as a liquid medium and an alkali developable polymer are added and dispersed. In addition, you may add another pigment dispersant as needed.

  The method for dispersing the pigment is not particularly limited as long as it is a conventionally known method. The obtained pigment dispersion may be used as it is, but it is preferable to remove coarse particles by centrifuging or passing through an arbitrary filter. Although the viscosity of the obtained pigment dispersion liquid is not specifically limited, It is 5-30 mPa * s, More preferably, it is 6-20 mPa * s.

  An example of the use of a pigment dispersion in an aqueous medium among pigment dispersions obtained by dispersing a pigment in a liquid medium is an aqueous inkjet colorant (ink). Specifically, as the use thereof, the resin-treated pigment obtained as described above is blended in an aqueous solution in which an alkali is dissolved so that the pigment content is 5 to 40% by mass. Accordingly, a water-soluble organic solvent is added, and further, a resin component to be a film component is added and dispersed by the above-described dispersion method to obtain a colorant.

  First, in the alkaline aqueous solution described above, the alkali serves to ionize the carboxy group of the A polymer block of the AB block copolymer of the present invention and dissolve the A polymer block in water. The amount of alkali used at this time may be about 0.5 to 1.5 times the molar equivalent of the carboxy group contained in the polymer block of A, and the carboxy group of the polymer block of A by this alkali. Neutralize and dissolve. Examples of the alkali used at this time include conventionally known alkalis such as ammonia, organic amines, and hydroxides such as sodium hydroxide. Here, preferably, ammonia or an organic amine is used. The reason is, for example, that alkali metal hydroxides such as sodium hydroxide are strong bases, and therefore, quaternary ammonium with the sulfonate salt of the dye of the above general formula (1) constituting the polymer block of B This is because the salt reacts with the hydroxide, the sulfonic acid becomes an alkali metal salt, the quaternary ammonium salt becomes a hydroxide salt, and the dye may be detached from the polymer.

  In the above, examples of the water-soluble organic solvent to be added as necessary include the above-mentioned alcohol solvents, glycol solvents, amide solvents, glycerin, and the like, and prevent ink drying and promote penetration into paper. Used for applications such as surface tension adjustment. Although the compounding quantity is arbitrary, it is used in the range of 0-50 mass% in the system.

  The resin component as the coating component used in the above is not particularly limited, and water-soluble polymers such as acrylic, acrylic styrene, ether urethane, carbonate urethane, and silicone, dispersions, and emulsions are used. . The addition amount is used in the range of 0 to 20% by mass in the dispersion, and is effective in improving adhesion to media, scratch resistance, and durability of printed matter.

  In the present invention, the above-mentioned pigments are used, and the desirable dispersed particle diameter of the pigment is as described above, and considering the ink color development and printing quality such as optical density and saturation, or sedimentation of the pigment in the ink. The organic pigment has an average particle diameter of 150 nm or less, and the inorganic pigment has a diameter of 300 nm or less. To obtain a pigment dispersion having a desired particle size distribution, reduce the size of the grinding media of the disperser, increase the filling rate of the grinding media, increase the processing time, slow the discharge speed, grinding A method such as classification using a post filter or a centrifuge is used. Or the combination of those methods is mentioned. Furthermore, it is possible to use a method of using a pigment in which the primary particle diameter of the pigment to be used is finely adjusted in advance by a conventionally known method, for example, a salt milling method. After dispersion, it is preferable to remove coarse particles with a centrifuge or a filter.

  Further, if necessary, additives are added to these colorants to form ink. As other additives, additives such as surfactants, pigment derivatives, dyes, leveling agents, antifoaming agents, ultraviolet absorbers and the like can be used, and there is no particular limitation. The surface tension is preferably in the range of 20 mN / m to 40 mN / m. A surfactant may be added at least from the viewpoint of expanding the dot diameter printed by the ink jet to an optimum width. As the surfactant, a conventionally known surfactant can be used. If the amount added is too large, the dispersion stability of the pigment may be impaired.

  The viscosity of the resulting dispersion is not particularly limited, but is 2 to 10 mPa · s for dye and organic pigment ink-jet inks and 5 to 30 mPa · s for inorganic pigment ink-jet inks. As described above, the pigment dispersion of the present invention can be obtained.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these examples. In the text, “part” or “%” is based on mass.

<Synthesis Example 1: Synthesis of AC block copolymer-1>
In a 1 L separable flask equipped with a reflux tube, a nitrogen gas introducing device, a thermometer, and a stirring device, 368.7 parts diethylene glycol monobutyl ether (hereinafter referred to as BDG) as an organic solvent, 3.2 parts iodine, methacrylic 44.0 parts of methyl acid (hereinafter referred to as MMA), 44.0 parts of butyl methacrylate (hereinafter referred to as BMA), 22.0 parts of 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHMA), 34.0 parts of poly (n = 2-4) ethylene glycol monomethyl ether methacrylate (manufactured by NOF Corporation, hereinafter referred to as PME200), 15.0 parts of methacrylic acid (hereinafter referred to as MAA), and diphenylmethane ( Hereinafter, 0.3 parts of DPM) and 2,2′-azobis (4-methoxy-2,4-dimethylvale) as a polymerization initiator. 13.5 parts of (nitrile) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as V-70) was charged and polymerized at 40 ° C. for 5.5 hours while flowing nitrogen to form a polymer block of A. When the solid content of the obtained polymer solution was measured, it was 32.3%, and the converted polymerization conversion was almost 100%. Further, when gel permeation chromatography (hereinafter referred to as GPC) measurement using tetrahydrofuran (hereinafter referred to as THF) as a developing solvent was performed, the number average molecular weight was 5700 and PDI was 1.26. When a part of this polymer solution was added to water, a resin precipitated. This indicates that the polymer obtained is insoluble in water.

  In addition, the resin acid value of the polymer block of A measured by titration with phenolphthalein as an indicator using a 0.1N KOH ethanol solution using ethanol / toluene as a solvent is 54.0 mgKOH / g, which is almost theoretical. It was as expected. Hereinafter, the acid value was measured by the same method as described above, and the value was shown.

  Next, the polymer block C was introduced into the polymer block A obtained above as follows. First, in the polymer solution obtained above, 30.1 parts of benzyldimethylammonium chloride ethyl methacrylate (hereinafter referred to as DMQ-1) having the structure of the general formula (2) and benzyl methacrylate (hereinafter referred to as BzMA) are represented. 88.1 parts) and 70.2 parts of BDG were mixed in advance and added. Further, 2.4 parts of V-70 was added and polymerized at the same temperature for 4 hours to form a polymer block of C. The obtained polymer solution had a solid content of 40.3%, and the converted polymerization rate was almost 100%. When GPC measurement was performed, the peak was small and unclear. This is considered to be due to the poor solubility of the quaternary ammonium salt in THF and the adsorption to the column.

  When a part of the polymer solution obtained above was added to water, it dissolved almost transparently. This is because the quaternary ammonium salt, which is a constituent component of the C polymer block, has a property of being dissolved in water. It is considered that the polymer block portion of A dissolved in water and insoluble in water was dispersed as fine particles. From this, it was suggested that the obtained polymer was an AC block copolymer in which a polymer block of C was introduced into a polymer block of A. This is referred to as AC block copolymer-1.

<Synthesis Example 2: Synthesis of AC block copolymer-2>
Using the same apparatus as used in Synthesis Example 1, 382.8 parts of BDG, 3.2 parts of iodine, 44.0 parts of MMA, 44.0 parts of BMA, 22.0 parts of 2-EHMA as an organic solvent Part, PME200 34.0 parts, MAA 15.0 parts, DPM 0.3 parts and V-70 13.5 parts as a catalyst. A block was formed. When the solid content of the obtained polymer solution was measured, it was 31.5%, and the converted polymerization conversion was almost 100%. The number average molecular weight measured by GPC was 5700, and PDI was 1.26. Moreover, the resin acid value of the polymer block of A was 54.5 mgKOH / g.

  Next, a solution in which 19.9 parts of DMQ-1, 88.1 parts of BzMA, and 46.4 parts of BDG were mixed and homogenized in advance was added to the polymer solution obtained above, and V-70 was further added. Polymerization was carried out in the same manner as in Synthesis Example 1 except that 2.2 parts were added to form a C polymer block. The obtained polymer solution had a solid content of 40.5%, and the converted polymerization rate was almost 100%.

  GPC measurement was performed in the same manner as in Synthesis Example 1. However, the peak was small and unclear, and it could not be measured well. Further, when a part of the obtained resin solution was added to water, it was slightly clouded and dissolved. This is probably because the amount of the quaternary ammonium salt is smaller than that in the case of Synthesis Example 1 and the solubility in water is lowered. However, since the polymer solution obtained showed solubility in water as compared with the polymer block of A being insoluble in water, it is considered that the desired AC block copolymer was obtained. It is done. This is referred to as AC block copolymer-2.

<Synthesis Example 3: Synthesis of AC block copolymer-3>
Using the same apparatus as used in Synthesis Example 1, 365.0 parts of BDG, 3.2 parts of iodine, 44.0 parts of MMA, 44.0 parts of BMA, and 22.2 parts of 2-EHMA as organic solvents. 0 parts, 34.0 parts of PME200, 15.0 parts of MAA, 0.3 parts of DPM as a catalyst, and 13.5 parts of V-70 were polymerized in the same manner as in Synthesis Example 1, A polymer block was formed. The obtained polymer solution had a solid content of 32.5%, and the converted polymerization rate was almost 100%. As a result of GPC measurement, the number average molecular weight was 5600 and PDI was 1.26. Further, the resin acid value of the polymer block of A was 54.3 mgKOH / g.

  Next, a solution obtained by previously mixing and homogenizing 42.0 parts of DMQ-1, 88.1 parts of BzMA, and 98.0 parts of BDG to the polymer solution obtained above was added, and V-70 was further added. Polymerization was carried out in the same manner as in Synthesis Example 1 except that 2.6 parts were added to form a C polymer block. The obtained polymer solution had a solid content of 40.0%, and the converted polymerization rate was almost 100%.

  GPC measurement was performed in the same manner as in Synthesis Example 1. However, the peak was small and unclear, and it could not be measured well. Moreover, when a part of the obtained resin solution was added to water, it was considered that an AC block copolymer was obtained because it was almost transparently dissolved. This is referred to as AC block copolymer-3.

  For the above Synthesis Examples 1 to 3, the number of moles of A monomer relative to 1 mol of the polymerization initiating compound, the number of moles of C monomer relative to 1 mol of the polymerization initiating compound, the mass ratio of the polymer block of A to the polymer block of C, 1 g of AC block copolymer The number of moles of the quaternary ammonium salt contained therein was summarized. This is shown in Table 1.

<Comparative Synthesis Example 1: Synthesis of comparative polymer by random copolymerization>
Using the same apparatus as used in Synthesis Example 1, 438.9 parts of BDG, 3.2 parts of iodine, 44.0 parts of MMA, 44.0 parts of BMA, 22.0 parts of 2-EHMA, 34.0 parts of PME200, 15.0 parts of MAA, 30.1 parts of DMQ-1, 88.1 parts of BzMA, 0.3 part of DPM as a catalyst, 13.5 parts of V-70, For 6 hours at 40 ° C. The solid content of the obtained polymer was 40.2%, and the converted polymerization rate was almost 100%. This is a comparative polymer randomly copolymerized with the same composition as the AC block copolymer of Synthesis Example 1.

<Example 1: Synthesis of dye polymer R-1>
A 3 L beaker was charged with 15 parts of Acid Red 289 (hereinafter referred to as AR-289, molecular weight 676.7) and 985 parts of water, and the mixture was stirred and homogenized. When a portion of this was spotted on a filter paper, it was confirmed that the dye had slipped through and the dye was dissolved. Next, when a mixed solution of 154.0 parts of the AC block copolymer-1 obtained in Synthesis Example 1 and 154.0 parts of ion-exchanged water was gradually added to the dye solution, thickening was observed. The mixture was stirred for 1 hour and a part of the resulting solution was spotted on a filter paper. As a result, resin precipitation was confirmed, and dye bleed was hardly observed. This is because the chloride ion of the quaternary ammonium salt chloride of the AC block copolymer and the sodium ion of AR-289 are eliminated as sodium chloride, while the quaternary ammonium salt and the sulfonate of AR-289. It is considered that the block copolymer was insolubilized by the formation of salts by the ions. That is, it is considered that a dye was introduced into the AC block copolymer, and an AB block copolymer having a structure defined in the present invention was obtained.

  When this solution was filtered, the filtrate was transparent, and even when washed with ion-exchanged water, the filtrate was transparent, suggesting that the dye was bound to the polymer. Then, it dried with 80 degreeC drying machine and grind | pulverized, and obtained AB block copolymer of this invention. This is referred to as dye polymer R-1. The content of the dye monomer unit in the AB block copolymer R-1 in which this dye is introduced is 26.4% in the AB block copolymer and 49.5% in the B block. It was. The polymer was measured with an infrared spectrophotometer (IR). The results are shown in FIG. 1, and a peak derived from the AC block copolymer and a peak derived from AR-289 were confirmed.

<Examples 2 and 3: Synthesis of dye polymers R-2 and 3>
Instead of the AC block copolymer-1 of Synthesis Example 1 used in Example 1, the AC block copolymer-2 obtained in Synthesis Example 2 and the AC block copolymer-3 obtained in Synthesis Example 3 were respectively obtained. The AB block copolymer of the present invention was synthesized in the same manner as in Example 1 except that it was used. Specifically, Example 2 was the same as Example 1 except that 228.0 parts of AC block copolymer-2 and 115.4 parts of AC block copolymer-3 were used as Example 3, respectively. Thus, an AB block copolymer was synthesized. In all examples, the amount of the polymer used was such that the quaternary ammonium salt of the AC block copolymer reacted in an approximately equimolar amount with respect to the sulfonic acid possessed by AR-289.

  In the obtained AB block copolymer, the same phenomenon as in Example 1 was observed, and it was confirmed that the AB block copolymer was an AB block copolymer. The AB block copolymer of Example 2 is referred to as dye polymer R-2, and the AB block copolymer of Example 3 is referred to as dye polymer R-3. The content of the dye monomer unit of the dye block copolymer R-2 was 18.8% in the AB block copolymer and 39.4% in the B block. Further, the content of the dye monomer unit of the dye block copolymer R-3 was 33.4% in the AB block copolymer and 58.0% in the B block.

<Example 4: Synthesis of dye polymer B-1>
A 3 L beaker was charged with 15 parts of Direct Blue 86 (hereinafter referred to as DB-86, molecular weight 780.2) and 985 parts of water, and the mixture was stirred and homogenized. The spot on the filter paper was seen through and it was confirmed that the dye was dissolved. Subsequently, when a mixed solution of 196.2 parts of the AC block copolymer-2 obtained in Synthesis Example 2 and 196.2 parts of ion-exchanged water was gradually added to the dye solution, the viscosity increased as in Example 1. Was confirmed. After stirring for 1 hour, spotting on the filter paper confirmed the deposition of the resin. There is almost no bleed, and most dyes are considered to have reacted. That is, it is considered that DB-86 dye molecules were introduced into the polymer block of C to form an AB block copolymer having a structure defined in the present invention. This is referred to as dye polymer B-1. The content of the dye monomer unit in this dye block copolymer was 20.7% in the AB block copolymer and 42.3% in the B block. This polymer was measured with an infrared spectrophotometer (IR). The results are shown in FIG. A peak derived from the AC block copolymer and a peak derived from DR-86 were confirmed.

<Example 5: Synthesis of dye polymer Y-1>
A 3 L beaker was charged with 15 parts of Direct Yellow 142 (hereinafter referred to as DY-142, molecular weight 794.7) and 985 parts of water, and the mixture was stirred and homogenized. The spot on the filter paper was seen through and it was confirmed that the dye was dissolved. Subsequently, when a mixed solution of 98.6 parts of the AC block copolymer-3 obtained in Synthesis Example 3 and 98.6 parts of ion-exchanged water was gradually added to the dye solution, the viscosity increased as in Example 1. Was confirmed. After stirring for 1 hour, spotting on the filter paper confirmed the deposition of the resin. There is almost no bleed, and most dyes are considered to have reacted. That is, it is considered that a dye molecule of DY-142 was introduced into the polymer block of C to form an AB block copolymer having a structure defined in the present invention. This is referred to as dye polymer Y-1. This polymer was measured with an infrared spectrophotometer (IR). The result is shown in FIG. The content of the dye monomer unit of this dye block copolymer was 36.1% in the AB block copolymer and 60.8% in the B block. The results are shown in FIG. A peak derived from the AC block copolymer and a peak derived from DY-142 were confirmed.

The dye polymers obtained in Examples 1 to 5 are shown together in Table 2.

<Synthesis Example 4: Synthesis of AC block copolymer-4>
Using the same apparatus as in Synthesis Example 1, 355.4 parts of triethylene glycol monobutyl ether (hereinafter referred to as BTG), 99 parts of BzMA, 22.7 parts of MAA and 0.27 parts of N-iodosuccinimide were used as organic solvents. 22 parts, 1.5 parts of iodine and 6.5 parts of V-70 were charged and polymerized for 5 hours in the same manner as in Synthesis Example 1 to form a polymer block of A. When the solid content was measured, it was 26.3%, and the converted polymerization conversion was almost 100%. The number average molecular weight was 6800, and PDI was 1.23. Similarly, the acid value was measured and found to be 121.7 mgKOH / g. Moreover, when this polymer solution was added to water, it was confirmed that it was precipitated, and it was confirmed that it was insoluble in water.

  Next, 25.4 parts of DMQ-1, 59.54 parts of BTG, and 79.2 parts of BzMA were charged and polymerized for 4 hours to form a polymer block of C. The solid content was 40.0%, and the converted polymerization rate was almost 100%. The molecular weight was unclear, and reliable molecular weight measurement could not be performed. Further, when this solution was added to water, it was confirmed that the translucent fine particles were dispersed. This is probably because the polymer A formed insoluble fine particles in water and the polymer block C dissolved in water. This is referred to as AC block copolymer-4.

<Synthesis Example 5: Synthesis of AC block copolymer-5>
In the same manner as in Synthesis Example 4, MAA was used as a monomer for forming the polymer block of A, but polymerization was carried out in the same manner as in Synthesis Example 4 except that the amount was reduced by half to form a polymer block of A. . The polymerization conversion was almost 100%, and the number average molecular weight of the obtained polymer was 5600, and PDI was 1.19. The acid value was 61.0 mgKOH / g.

  Next, polymerization was carried out with the same composition as in Synthesis Example 4 to form a polymer block of C. The solid content was 40.2%, and it was confirmed that the polymerization was almost 100%. The molecular weight was unclear. Further, when this solution was added to water, it was confirmed that the translucent fine particles were dispersed. This is referred to as AC block copolymer-5.

<Synthesis Example 6: Synthesis of AC block copolymer-6>
As in Synthesis Example 4, MAA was used as a monomer for forming the polymer block of A. Polymerization was performed in the same manner as in Synthesis Example 4 except that the amount was doubled to form a polymer block of A. The polymerization conversion was almost 100%, and the number average molecular weight of the obtained polymer was 7800, and PDI was 1.35. The acid value was 205.0 mgKOH / g.

  Next, polymerization was carried out with the same composition as in Synthesis Example 4 to form a polymer block of C. The solid content was 40.2%, and it was confirmed that the polymerization was almost 100%. The molecular weight was unclear. Further, when this solution was added to water, it was confirmed that the translucent fine particles were dispersed. This is referred to as AC block copolymer-6.

  For the synthesis examples 4 to 6, the acid value of the polymer block of A, the number of moles of the A monomer with respect to 1 mol of the polymerization initiating compound, the number of moles of C monomer with respect to 1 mol of the polymerization initiating compound, the mass ratio of the polymer block of A and the polymer block of C The number of moles of the quaternary ammonium salt contained in 1 g of the AC block copolymer was summarized. This is shown in Table 3.

<Example 6: Preparation of treated blue pigment-1>
In a 5-liter flask, 347.2 parts (pigment content) of an aqueous paste of refined PB-15: 6 (A-037, manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 28.8%, average primary particle size 30 nm) 100 parts), and 5.0 parts of copper phthalocyanine monosulfonic acid (molecular weight 656.1, acting as a pigment synergist while acting as a pigment having a sulfonic acid characterizing the present invention, hereinafter referred to as MS) And diluted with water to a pigment concentration of 5%. While stirring with a homogenizer, 15.0 parts of AR-289 was added and stirred at 5000 rpm for 1 hour to peptize. A part of it was picked and spotted on a filter paper.

  Next, a mixed solution of 205.5 parts of the AC block copolymer-1 obtained in Synthesis Example 1 and 205.5 parts of ion-exchanged water was gradually added to the dye solution containing the pigment prepared above. . It was confirmed that the viscosity increased at a certain point and then decreased. This thickening is caused by the salt exchange of the AC block copolymer dissolved in water by having a quaternary ammonium salt with the sulfonate salt of AR-289 and MS, so that the polymer block of C becomes B This is considered to be because the polymer block was deposited on the pigment surface and the pigment surface became hydrophobic due to the AB block copolymer resulting in no fluidity. Next, the mixture was stirred as it was for 1 hour, and a part was taken again and spotted on a filter paper. The results are shown in FIG. 4 together with those at the time of peptization.

  The left side of FIG. 4 is spotted at the time of peptization, and it can be seen that the center is a pigment and the dye AR-289 is bleed around it. The right side of FIG. 4 clearly showed no bleed of AR-289 after addition of the AC block copolymer. From these facts, it is considered that the AC block copolymer and AR-289 were salt-exchanged to insolubilize the dye, resulting in an AB block copolymer as defined in the present invention and a pigment treated.

  The solution was then filtered and washed. Filtration was fast, and there was no coloring of the filtrate or the washing solution. Also from this, it is presumed that it is an AB block copolymer. Subsequently, it dried at 80 degreeC for 24 hours, and grind | pulverized in the mill.

  This pulverized product is theoretically about 100.0% with respect to 100 parts of the pigment used, and MS and AR-289 as dyes react with the AC block copolymer to remove sodium chloride. A pigment treated with an AB block copolymer. Moreover, in said example, the quaternary ammonium salt of AC block copolymer was made to react with MS and the sulfonic acid group of AR-289 by substantially equimolar. This is referred to as treated blue pigment-1.

  In the treated blue pigment-1 obtained above, the dye monomer unit represented by the general formula (1) characterizing the present invention is 26.5% in the AB block copolymer and 49. 49% in the B polymer block. The ratio of the AB block copolymer used for the treatment with respect to 100 parts of pigment was 101.2%, and the pigment content contained in the obtained resin-treated pigment was 49.7%. is there. All of these contents are theoretically calculated values. This point will be briefly described below.

  5 g of MS used (in the following explanation, the part is treated as “g”) is 7.6 mmol. Similarly, since AR-289 is used at 22.2 mmol (15 g), all sulfonic acid groups Is 29.8 mmol. On the other hand, since 82.8 g of the AC block copolymer was used in the polymer content, the quaternary ammonium salt contained in the polymer was 29.8 mmol, which was equimolar with all sulfonic acid groups of MS and AR-289. It becomes. By reacting this, MS-derived dehydrochlorination was 7.6 mmol (0.28 g), and AR-289-derived desodium chloride was 22.2 mol (1.30 g), for a total loss of 1.58 g. . Thus, the amount of AB block copolymer is 5 + 15 + 82.8−0.28−1.30 = 101.2 g, ie, 100 parts pigment is treated with about 101.2 parts AB block copolymer. It will be. As a result, the ratio of the pigment contained in the treated pigment is 49.7%.

  On the other hand, regarding the dye monomer unit represented by the general formula (1) in the AB block copolymer obtained by the reaction, the molecular weight of methacrylate (hereinafter referred to as MS methacrylate) obtained by reacting MS is 903. On the other hand, the molecular weight of methacrylate (hereinafter referred to as AR-289 methacrylate) obtained by reacting AR-289 is 902.1. In Example 6, since MS and AR-289 all react with the AC block copolymer, the resulting AB block copolymer is introduced with the moles of MS and AR-289 used. . That is, 6.9 g of MS methacrylate and 20.0 g of AR-289 methacrylate are introduced into the AB block copolymer, and the total amount of the dye-containing methacrylate is 26.9 g. Since the AB block copolymer obtained as described above is 101.2 g, the dye-containing methacrylate (dye monomer unit) contained in the AB block copolymer is 26.5%.

  Moreover, in Example 6, since the ratio of the polymer block of A and the polymer block of C of the used AC block copolymer (solid content 40.3%) is 57:43, the used AC block polymer The polymer block of A contained in (205.5 g) is 47.2 g. The content of the polymer block of A in the AB block copolymer is the same as that of the AC block polymer and remains 47.2 g. Therefore, the polymer block of B in 101.2 g of the produced AB block copolymer The content of is 54.0 g. Since the above-mentioned pigment-containing methacrylate is 26.9 g, 26.9 ÷ 54.0 × 100 = 49.8%. Hereinafter, calculation was performed in the same manner.

<Example 7: Preparation of treated blue pigment-2>
In the same manner as in Example 6, instead of the AC block copolymer-1 obtained in Synthesis Example 1, the AC block copolymer-2 (solid content 40.5%) obtained in Synthesis Example 2 was changed to 306. A resin-treated pigment was prepared in the same manner as in Example 6 except that 6 parts were used to obtain a pulverized product. As a result, the same phenomenon as in Example 6 was observed, and it was confirmed that the pigment was treated with the AB block copolymer.

  According to the same theoretical calculation as in Example 6, the obtained resin-treated pigment is a pigment theoretically treated at about 142.6% with an AB block copolymer with respect to 100 parts of pigment. Also in the above example, the quaternary ammonium salt of the AC block copolymer was reacted with MS and the sulfonic acid group of AR-289 in an approximately equimolar amount. This is referred to as treated blue pigment-2.

<Examples 8 to 10: Preparation of treated blue pigments 3 to 5>
In the same manner as in Example 6, instead of the AC block copolymer-1 obtained in Synthesis Example 1, the AC block copolymer-3 (solid content 40.0%) obtained in Synthesis Example 3 was used. The resin-treated pigments (pulverized products) of Examples 8 to 10 were prepared in the same manner as Example 6 except that they were used in the following amounts. Specifically, the AC block copolymer-3 obtained in Synthesis Example 3 was used in an amount of 155.2 parts in Example 8, and in an amount of 194.0 parts in Example 9. Example 10 was used in an amount of 232.8 parts. In all cases, the same phenomenon as in Example 6 was observed, and it was confirmed that the pigment was treated with the AB block copolymer.

  According to the theoretical calculation values similar to those of Example 6, the resin-treated pigment obtained in Example 8 was theoretically about 80.5 parts (80.5 parts) of AB block copolymer with respect to 100 parts of pigment. %). Also in this example, the quaternary ammonium salt of the AC block copolymer was reacted with sulfonic acid groups of MS and AR-289 in an approximately equimolar amount. This is referred to as treated blue pigment-3.

  According to theoretical calculation values similar to those of Example 6, the resin-treated pigment obtained in Example 9 was theoretically about 96.0 parts (96.0 parts) in terms of AB block copolymer with respect to 100 parts of pigment. %). In this example, the quaternary ammonium salt of the AC block copolymer was reacted with the sulfonic acid group of AR-289 under a 1.25 molar excess, and the quaternary ammonium salt remained. It is. This is referred to as treated blue pigment-4.

  According to theoretical calculation values similar to those in Example 6, the resin-treated pigment obtained in Example 10 was theoretically about 111.6 parts (111.6 parts) in an AB block copolymer with respect to 100 parts of pigment. %). In this example, the quaternary ammonium salt of the AC block copolymer was reacted with the sulfonic acid group of AR-289 in an excess of 1.5 molar times, and the quaternary ammonium salt remained. It is. This is referred to as treated blue pigment-5.

<Comparative Example 1: Preparation of comparatively treated blue>
A resin-treated pigment of a comparative example was prepared in the same manner as in Example 6 except that the random block copolymer solution having the same composition as that of Synthesis Example 1 obtained in Comparative Synthesis Example 1 was used. The same phenomenon as in Example 6 was observed, and the resin treatment of the pigment was possible even with the random copolymer. From this, the action of the desalting reaction itself occurred in the same way with the random copolymer, and the pigment could be treated. It was confirmed that there was. This is referred to as a comparatively treated blue pigment.

  Regarding Examples 6 to 10 and Comparative Example 1 obtained above, the content and B in the AB block copolymer of the dye-containing methacrylate (dye monomer unit) represented by the general formula (1) characterizing the present invention Table 4 summarizes the content of the polymer block in the polymer block, the ratio of the AB block copolymer (dye polymer) to the pigment, and the ratio of the pigment-derived component contained in the resin-treated pigment. In addition, about the comparative example 1, it is a ratio in a random copolymer.

<Application example: Colorant for color filter>
The resin-treated pigments obtained in Examples 6 to 10 and Comparative Example 1 were blended in the amounts (parts) shown in Table 5 and stirred with a dissolver for 2 hours. After confirming that the lump of pigment has disappeared, use a horizontal media disperser “Dynomill 0.6 liter ECM type” (trade name, manufactured by Shinmaru Enterprises Co., Ltd., zirconia bead diameter: 0.65 mm). A pigment dispersion was prepared by a dispersion treatment at 10 m / s. These were designated as Application Examples 1 to 5 and Comparative Application Example 1, respectively. In addition, as an example simulating normal dispersion of a conventionally known colorant, PB-15: 6 (hereinafter referred to as a comparative blue pigment) treated with copper phthalocyanine monosulfonic acid 5% is used as a commercially available pigment dispersant. Was used in the same manner as in the prior art, and this was designated as Comparative Application Example 2. Table 5 summarizes the composition of the pigment dispersion.

  In each of the pigment dispersions obtained above, after measurement of the number average particle diameter of the pigments contained in the pigment dispersion, the initial viscosity of the pigment dispersion, and after standing at 45 ° C. for 10 days (after storage) Table 6 shows the measurement results of the viscosities. The average particle size was measured with a particle size measuring instrument “NICOMP 380ZLS-S” (trade name, manufactured by International Business Corporation). Hereinafter, it carried out similarly.

  As shown in Table 6, the pigment dispersion using the resin-treated pigment of the present invention showed good dispersibility and storage stability. On the other hand, since the resin-treated pigment of Comparative Example 1 has a random structure, it was confirmed that although the resin treatment was possible, the same effect as obtained in the examples of the present invention could not be exhibited. This is presumably because the polymer structure adsorbs to the inter-particle pigment, or conversely aggregates the pigment because of the random structure. Moreover, as shown in Table 6, the pigment dispersion using the resin-treated pigment obtained by treating the pigment with the dye block copolymer of the present invention is used for a normal colorant, that is, in Application Comparative Example 2, It was confirmed that the same dispersibility and storage stability as in the case of a pigment dispersion obtained by dispersing a pigment with an ordinary pigment dispersant can be achieved. In addition, when the resin-treated pigment of the example of the present invention is used, the pigment can be finely dispersed and the stability thereof can be maintained without adding an acrylic resin solution as a dispersion resin. It was confirmed. Moreover, it turned out that there exists a tendency for a viscosity to go out high from the result of the application examples 3-5 because many quaternary ammonium salts remain | survive. However, the storage stability is good and there is no problem.

  In addition, the average particle diameter of the pigment contained in the pigment dispersion of the application example using the resin-treated pigment of the example of the present invention is about 50 nm or less, and the refined pigment is sufficiently finely dispersed. It was confirmed that In addition, the pigment dispersion of any application example has an initial viscosity of about 10 mPa · s, and it is clear that the change in viscosity is small when the initial viscosity and the viscosity after storage are compared. As a result, it was confirmed that the pigment dispersion of the application example has sufficient stability.

(Application Examples 6 and 7, Comparative Application Example 3: Preparation of pigment colorant for pseudo color filter)
Next, using the pigment dispersions obtained in the above-mentioned application examples 1 and 2 and comparative application example 2 respectively, they are blended in the amounts (parts) shown in Table 7 and thoroughly mixed with a mixer to prepare a blue pseudo A pigment colorant (pseudo color resist) for color filters was obtained.

  The “photosensitive acrylic resin varnish” in Table 7 was a varnish containing an acrylic resin obtained by reacting glycidyl methacrylate with a BzMA / MAA copolymer. Mn of this acrylic resin was 6000, PDI was 2.38, and the acid value was 110 mgKOH / g. “TMPTA” represents trimethylolpropane triacrylate, “HEMPA” represents 2-hydroxyethyl-2-methylpropionic acid, and “DEAP” represents 2,2-diethoxyacetophenone.

Next, the glass substrate treated with the silane coupling agent was set on a spin coater. The pigment colorant for pseudo color filter prepared in Application Examples 6 and 7 and Comparative Application Example 3 was spin-coated on a glass substrate at 300 rpm for 5 seconds. And after performing prebaking for 10 minutes at 120 degreeC, it exposed by the light quantity of 100 mJ / cm < ² > using the ultrahigh pressure mercury lamp, and manufactured each blue glass substrate.

  Each of the obtained glass substrates (hereinafter referred to as a color glass substrate) had excellent spectral curve characteristics. FIG. 5 shows the spectral curves of the coating film of Comparative Application Example 3 using the comparative blue pigment of Comparative Application Example 2 and the coating films of Application Examples 6 and 7 using the resin-treated pigment of the present invention. Indicated. As a result, as shown in FIG. 5, absorption derived from the dye block copolymer of the present invention was confirmed.

  The glass substrate before exposure was allowed to stand at 250 ° C. for 1 hour, and the change in transmittance was examined. The result is shown in FIG. As a result, in the case of the pigment colorant for pseudo color filter of Application Examples 6 and 7 using the resin-treated pigment of the present invention, the decrease in transmittance due to heat is small, whereas in the case of Comparative Application Example 3, It can be seen that the rate is decreasing. This is because the surface of the pigment particle is treated with the AB block copolymer (dye block copolymer) of the present invention, and in particular, it is treated with the polymer block of B having ionic properties, so that its heat resistance is good. It is thought that it became. Moreover, since the dye was polymerized in the pigment block copolymer of the present invention, it was also confirmed that there was no volatilization of the dye due to heat.

  Next, an alkali developability test was conducted as follows. That is, 5N of 0.1N tetramethylammonium hydroxide aqueous solution was applied to a color glass substrate that had been pre-baked by spin coating using the pigment colorants for pseudo color filters of Application Examples 6 and 7 and Comparative Application Example 3. Spotting was performed every second, and a development test such as “how many seconds later the exposed part of the coating film was dissolved” was performed. The results are shown in Table 8.

  As shown in Table 8, when the colorants of Application Examples 6 and 7 using the resin-treated pigment of the present invention were used, the development time was longer than when the colorant of Comparative Application Example 3 was used. A short result was obtained. Also, the dissolution behavior did not cause film-like residue, and the edges of the coating film that remained without being dissolved were observed with a microscope and confirmed to be sharp. This is presumably because the polymer block A of the resin-treated pigment was neutralized with alkali and the polymer B was adsorbed to the pigment, so that it was dissolved in water and developability was improved. On the other hand, when the colorant of Comparative Application Example 3 was used, it took a little time to dissolve, and it was confirmed that the dissolution behavior was not only detached as a small film, but also some edges remained. These are considered to be because the pigment dispersant cannot be alkali-developed with the colorant of Comparative Application Example 3. That is, it is expected that the development time can be shortened and the productivity can be improved by using the colorant using the resin-treated pigment of the present invention.

(Comparative Application Example 4)
Next, using a refined product of dioxazine-based violet pigment PV-23 and a pigment obtained by treating copper phthalocyanine monosulfonic acid with 5% of the pigment (hereinafter referred to as “comparative violet pigment”), a comparative application example In the same manner as in No. 2, a commercially available pigment dispersant was dispersed to prepare a comparative violet pigment dispersion. This is a comparative pigment dispersion that simulates the dispersion of a conventionally known colorant. Using this comparative pigment dispersion, PB-15: 6 used in Comparative Application Example 2 shown in Table 5 was adjusted so that the ratio of PB-15: 6 to PV-23 was 85:15. A pigment dispersion was prepared in the same manner as Comparative Application Example 2 except that it was blended. Using the obtained pigment dispersion, a blue pigment colorant for pseudo color filter (pseudo color resist) was obtained in the same manner as in Comparative Application Example 3, and this was designated as Comparative Application Example 4.

Using the obtained colorant of Comparative Application Example 4, spin coating was performed on a glass substrate in the same manner as described above. Then, after pre-baking at 90 ° C. for 2 minutes, post-baking was performed at 230 ° C. for 30 minutes, and exposure was performed with a light amount of 100 mJ / cm ² using an ultra-high pressure mercury lamp to produce a blue glass substrate.

  The Y value, which is an index of contrast (CR) and transparency, was measured during the bribaking and postbaking. Specifically, the contrast (CR) and Y value, which is a transparency index, were measured with a contrast measuring machine (contrast tester CT-1 manufactured by Osaka Electronics Co., Ltd.), with y = 0.074. The results are shown in Table 9. In addition, the measurement result was shown relatively with the CR and Y values of prebaking when the colorant of Comparative Application Example 4 was used as 100%. Table 9 also shows each value when the colorants of Application Examples 6 and 7 were used.

  As shown in Table 9, in the case of the colorants of Application Examples 6 and 7 using the resin-treated pigment of the present invention, compared to the colorant of Comparative Application Example 4 using a normal pigment dispersion, High contrast and high transparency can be obtained in the coloring and transparency derived from the dye. Moreover, the heat resistance was good, and even if the temperature was high, there was almost no decrease in physical properties.

Next, using the blue glass substrates obtained in Application Examples 6 and 7 and Comparative Application Example 4, respectively, a light resistance test was performed with a super UV tester. Irradiation was performed at 60 mW / cm ² for 30 hours, and the color difference before and after irradiation was measured. The color difference ΔE of the blue glass substrate using the conventional colorant obtained in Comparative Application Example 4 was 0.2, confirming light resistance derived from the pigment. On the other hand, the color difference ΔE of the blue glass substrate using the colorant containing the resin-treated pigment of the present invention is 0.4 in the application example 6 and 0.4 in the application example 7, and is more light resistant than the comparative application example 4. Although the results were poor, the light resistance was sufficiently high and suitable for use, and there was no particular problem.

  As described above, the colorant formed using the resin-treated pigment of the example of the present invention is found to be excellent in dispersibility, storage stability, optical properties, heat resistance, alkali developability, and light resistance, It has been shown to be very useful as a colorant for color filters.

<Example 11: Preparation of treated cyan pigment-1>
A 5-liter flask was charged with 337.8 parts of a PB-15: 3 (A-220JC, manufactured by Dainichi Seika Kogyo Co., Ltd.) water paste (solid content 29.6%), and further a surfactant having a sulfonic acid group. After adding 1.5 parts of sodium dodecylbenzenesulfonate (molecular weight 348.5, hereinafter also referred to as “SDS”) and 59.2 parts of ion-exchanged water, the mixture was stirred with a disper to prepare a mill base. Next, using the horizontal media disperser described above, the pigment was sufficiently dispersed in the mill base in the same manner to obtain a pigment dispersion.

  The pigment dispersion obtained above was diluted with water to a pigment concentration of 5%. While stirring with a homogenizer, 15 parts of Direct Blue 199 (Sirius Turcoise S-FBL, manufactured by Dystar Japan, hereinafter DB-199, theoretical molecular weight 909.4, having one sodium sulfonate group in the average molecule) Prepared. After stirring at 5000 rpm for 1 hour to remove the pigment and dye, a part was taken and spotted on a filter paper. Next, an aqueous solution obtained by mixing 144.4 parts of the solution of the AC block copolymer-1 obtained in Synthesis Example 1 and 144.4 parts of ion-exchanged water and gradually adding the solution was gradually added. It was confirmed that it was sticky. Subsequently, it stirred as it was for 1 hour. Thereafter, a part of the solution was spotted, and the result was shown in FIG.

  FIG. 7 shows the state of the surface of the spot, and the left one is the spot when the pigment and dye are peptized. The central pigment and the bleed dye can be confirmed. In addition, the right one is spotted after adding the AC block copolymer and thickening, but dye bleed cannot be confirmed. From this, it was confirmed that the chloride ion of the AC block copolymer and the sodium ion of the dye caused a desalting reaction to form an AB block copolymer, insolubilized and precipitated, and the pigment was processed. did it. The result of FIG. 7 is inferred that the pigment was treated with the AB block copolymer.

  Subsequently, when it was filtered and washed well with water, the filterability was very good, and it was confirmed that it was transparent and the dye did not flow. From this, it is considered that the AB block copolymer of the dye polymer defined in the present invention was formed and the pigment was processed. A resin-treated pigment was thus obtained, and the solid content of the water paste was 35.5%. The resin-treated pigment prepared above is prepared in an aqueous solvent having a pigment finely dispersed in SDS, which is a surfactant having a sulfonic acid group, so that the treated pigment is also in a fine state. It is intended to be processed. In this case, dodecylbenzenesulfonic acid (SDS) used as a dispersant is also considered to contribute to adsorption by salt exchange with some of the AC block copolymers. For this reason, those with SDS introduced are not treated as dyes, but are treated as AB block copolymers because they contain monomers that have undergone a salt exchange reaction.

  According to the same theoretical calculation value as in Example 6 described above, the resin-treated pigment obtained above is theoretically treated with AB block copolymer at about 73.1% with respect to 100 parts of pigment. Pigment. In addition, although SDS was introduced as described above, it was not treated as a pigment, but was assumed to be an AB block copolymer. In addition, the quaternary salt of the AC block copolymer is reacted with sulfonic acid groups of SDS and DB-199 in an approximately equimolar amount. This is referred to as treated cyan pigment-1. In this treated cyan pigment-1, the content of the dye-containing methacrylate (dye monomer unit) defined in the present invention in the AB block copolymer is 32.3%, and the content of B in the polymer block is 46. Furthermore, the AB block copolymer with respect to 100 parts of pigment is 73.1 parts, and the pigment content contained in the treated pigment is 57.8%.

(Application Example 8: Preparation of cyan aqueous pigment dispersion)
After mixing 487.3 parts of the water paste of the treated cyan pigment-1 obtained above, 20 parts of BDG, 5 parts of diethanolamine, and 43.3 parts of ion-exchanged water, the mixture was stirred with a disper to prepare a mill base. At first, it was in a state without fluidity, but fluidity came out as it was stirred. After sufficiently mixing, the above-mentioned horizontal media disperser was then used for dispersion treatment at a peripheral speed of 10 m / s to sufficiently disperse the pigment in the mill base. The obtained mill base was filtered through a 10 μm membrane filter, and then filtered through a 5 μm membrane filter. At this time, no clogging of the filter was observed. Ion exchange water was added to adjust the pigment content to 15% by mass to obtain a cyan aqueous pigment dispersion defined in the present invention. The number average particle diameter of the pigment contained in the obtained cyan aqueous pigment dispersion was 103 nm and was finely dispersed. The viscosity was 3.30 mPa · s at 25 ° C. and 60 rpm when measured using an E-type viscometer, indicating a low viscosity despite a high resin content being processed for the pigment. It was. The reason is considered that there is no dissolved polymer component.

(Comparative Application Example 5: Preparation of comparative cyan aqueous pigment dispersion)
In order to compare with the cyan aqueous pigment dispersion obtained above, the above PB-15: 3 pigment was dispersed using a conventionally known dispersant to prepare a comparative cyan aqueous pigment dispersion. Specifically, a styrene maleic acid copolymer (acid value 200 mg KOH / g, number average molecular weight 5000, PDI 2.3, diethanolamine neutralized aqueous solution, solid content 25%), which is a random polymer type dispersant, is used as the dispersant. Then, a comparative cyan aqueous pigment dispersion was obtained by dispersing in the same manner as in Application Example 8 except that 30 parts of the dispersant was used in a solid content with respect to 100 parts of the pigment. The number average particle diameter of the pigment contained in the obtained comparative cyan aqueous pigment dispersion was 99 nm and was finely dispersed. Moreover, when measured using an E-type viscometer, the viscosity was 3.69 mPa · s at 25 ° C. and 60 rpm.

  Application Example 8 The storage stability test of the obtained cyan aqueous pigment dispersion and the comparative cyan aqueous pigment dispersion obtained in Comparative Application Example 5 was carried out by the following method. Each dispersion was placed in a glass bottle and placed in a thermostatic chamber set at 70 ° C., and the viscosity and average particle size were tested after standing for 1 week. As a result, the average particle diameter of the cyan aqueous pigment dispersion using the resin-treated pigment of the present invention is 103 nm, the viscosity is 3.21 mPa · s, and no change in physical properties due to storage is observed. It was confirmed that the sex was retained. This is considered to be because the AB block copolymer of the present invention is markedly adsorbed on the pigment to enhance the storage stability. On the other hand, the comparative cyan aqueous pigment dispersion had an average particle size of 135 nm and a viscosity of 5.6 mPa · s, and the pigment was agglomerated, thickened, and storage stability was poor.

  Next, using both pigment dispersions, the remaining amount of water was adjusted so that the cyan pigment content was 3%, BDG 1.8%, 1,2-hexanediol 5%, glycerin 15%, and Surfynol 465 1%. The ink was made by adjusting with. And the average particle diameter of the pigment in each ink, a viscosity, and a storage stability test were done by the above-mentioned method. The results are shown in Table 10.

  From the above results, it was confirmed that the ink using the treated pigment of the present invention is excellent in long-term storage stability as in the case of the pigment dispersion.

  Next, each of the inks prepared above was loaded into a cartridge and solid-printed with a printer to evaluate printability. At this time, the printer uses a photographic glossy paper (PGPP), Xerox paper 4024 manufactured by Xerox Corporation in the US, and a dedicated photo matte paper in a printing mode of 720 dpi using an ink jet printer EM930C manufactured by Seiko Epson Corporation. Solid printing was performed. As a result, in the ink using the cyan aqueous pigment dispersion of the invention of Application Example 8, no streaks, twists, missing dots, etc. were confirmed even after printing for a long time. In addition, it was confirmed that the nozzle could be discharged without any problem from the Ingchette nozzle. On the other hand, in the ink using the comparative cyan aqueous pigment dispersion, it was confirmed that streaks were generated after 10 sheets. This is probably because the dissolved dispersant is a random polymer dispersant, and thus the viscosity is poor. From the above results, it was confirmed that the ink of the application example using the resin-treated pigment of the present invention has good ejection stability.

  In addition, printing was performed with plain paper instead of photomat paper. The same image quality was obtained with both inks, and no change was seen when water drops were dropped. That is, when a dye that dissolves in water, such as a dye, is used as an inkjet ink (hereinafter referred to as IJ ink), the dye dissolves in water droplets and causes bleeding, but in the case of using the dye polymer of the present invention, the dye Since the pigment | dye which is is couple | bonded with the polymer, it is thought that the bleeding etc. did not arise with water. From the above results, it was confirmed that the ink of the application example of the present invention has good water resistance.

  In addition, after the above ink printing test, each ink-jet ink head is dried at 45 ° C. for 24 hours so that the ink is dried by the head so that it cannot be ejected. Thereafter, the head cleaning operation of the printer is performed once. The re-ejectability was evaluated. The ink using the cyan aqueous pigment dispersion of the invention of Application Example 8 could be ejected without any problem. That is, it is apparent that the pigment dispersion of the present invention is once dried, the dried product is dissolved and dispersed again, and re-dissolvability and re-dispersibility are good. This is presumably because the polymer block of A contains a carboxyl group and is ion-neutralized to form ions and easily dissolves in a liquid medium such as water even when dried. From this, it was confirmed that the pigment treated with the AB block copolymer of the present invention has good re-solubility due to the effect of the polymer block of A.

  Moreover, the hue of the printed matter of each photomat paper obtained above was measured by optical density (“Macbeth RD-914”, trade name, manufactured by Macbeth) and evaluated. As a result, compared with the printed matter formed with the ink using the pigment dispersion liquid of Comparative Application Example 5, the printed matter formed with the ink using the pigment dispersion liquid of the present invention has excellent color development and an expanded color range. I found out.

<Example 12: Preparation of treated magenta pigment-1>
Into a 5 liter flask, 333.3 parts of a water paste (solid content: 30.0%) of PR-122 (CFR-130P, manufactured by Dainichi Seika Kogyo Co., Ltd.) was added, and water was added so that the pigment concentration would be 5%. Diluted. Next, 12 parts of AR-289 were charged while stirring with a homogenizer. After stirring at 5000 rpm for 1 hour to remove the pigment and dye, a part was taken and spotted on a filter paper. Next, 110.8 parts of the solution of the AC block copolymer-4 obtained in Synthesis Example 4 and 110.8 parts of ion-exchanged water were mixed and homogenized aqueous solution was gradually added. It was confirmed that it was sticky. Subsequently, it stirred as it was for 1 hour. Then, a part of the solution was taken and spotted on a filter paper, and the result was shown in FIG.

  As shown in FIG. 8, the same result as in the case of Example 11 shown in FIG. 7 is shown, and the left one is a spot when the pigment and the dye are peptized. In addition, the bleeding dye can be confirmed. The right one is spotted after adding AC block copolymer and thickening. Since the bleed of the dye cannot be confirmed, the chloride ion of the AC block copolymer and the sodium ion of the dye undergo a desalting reaction to form an AB block copolymer, which is insolubilized and precipitated to treat the pigment. I was able to confirm.

  It was then filtered and washed thoroughly with water. The filterability was very good, and it was confirmed that it was transparent and no dye was flowing. From this, it is considered that the AB block copolymer of the dye polymer defined in the present invention was formed and the pigment was processed. In this way, a resin-treated pigment was obtained, and the solid content of this water paste was 33.3%. This is referred to as treated magenta pigment-1.

  According to the same theoretical calculation value as in Example 6 described above, the resin-treated pigment obtained above was obtained by reacting AR-289 with an AC block copolymer with respect to 100 parts of pigment. A pigment theoretically treated with a B block copolymer at about 55.3%. The pigment content contained in the resin-treated pigment is 64.4%. Further, the quaternary salt of the AC block copolymer was reacted with the sulfonic acid of AR-289 in an approximately equimolar amount. Further, the content of the dye-containing methacrylate of the present invention in the AB block copolymer is 28.9%, and the content of B in the polymer block is 49.2%.

<Examples 13 and 14>
Instead of the A-C block copolymer-4 obtained in Synthesis Example 4 used in Example 12, 105.0 parts of the A-C block copolymer-5 obtained in Synthesis Example 5 was used in Example 13. In Example 14, resin-treated magenta pigments were prepared in the same manner as in Example 12 except that 122.3 parts of the AC block copolymer-6 obtained in Synthesis Example 6 was used. In any case, the same phenomenon as in Example 12 was observed, and it was confirmed that the pigment was treated with the AB block copolymer, and the resin-treated pigment defined in the present invention was obtained. The product obtained in Example 13 is referred to as treated magenta pigment-2, and the product obtained in Example 14 is referred to as treated magenta pigment-3. Further, the ratio of the AB block copolymer to 100 parts of the pigment, the pigment content contained in the resin-treated pigment, the content of the dye-containing methacrylate (dye monomer unit) in the AB block copolymer, the dye content in the B block copolymer The contents of methacrylate are shown in Table 11 together with Example 12.

(Application Example 9: Preparation of magenta pigment dispersion and ink using the same)
In the same manner as in Application Example 8, using the treated magenta pigment-1, the treated magenta pigment-2 or the treated magenta pigment-3 obtained in Examples 12-14, respective pigment dispersions were prepared, Using this, each ink was prepared in the same manner as in Application Example 8. All of these pigment dispersions and inks are the same as in the case of the cyan aqueous pigment dispersion using the resin-treated pigment of the present invention and the ink using the same in Application Example 8. It was confirmed that all showed good performance in terms of discharge property, ejection stability and re-dissolvability. From this, even when the polymer block of A has various acid values, the AB block copolymer of the present invention showed the same excellent effect, and the usefulness of the resin-treated pigment of the present invention was confirmed.

(Comparative Application Example 6: Preparation of comparative magenta pigment dispersion and comparative ink using the same)
For comparison with the above magenta pigment dispersion, a comparative magenta pigment dispersion was prepared. Specifically, a comparative magenta pigment dispersion was obtained in the same manner as in Comparative Application Example 5 except that PR-122, which is a magenta pigment, was used instead of PB-15: 3 used in Comparative Application Example 5. . A comparative magenta ink was prepared in the same manner.

  Using the ink prepared using the treated magenta pigment-1 obtained in Application Example 9 and the comparative magenta ink obtained in Application Comparative Example 6, printing was performed with an inkjet printer in the same manner as in Application Example 8, and the printing was performed. The product was measured for the hue and optical density ("Macbeth RD-914" trade name, manufactured by Macbeth) of the printed matter of photomat paper. As a result, it was found that when the pigment dispersion of the present invention was used, the color development was excellent and the color range was expanded as compared with the comparative example.

(Application Example 14: Application to UV-curable IJ ink colorant)
The application to the colorant for ultraviolet curable IJ ink was examined. 40 parts of the treated cyan pigment-1 obtained above (pigment content 20 parts) and 60 parts of isobornyl acrylate were added and mixed, and the mixture was stirred with a dissolver for 2 hours. After confirming that the lump of the pigment had disappeared, the pigment dispersion was prepared by carrying out dispersion treatment using the above-mentioned horizontal media disperser. The obtained pigment dispersion was passed through a 10 μm filter and a 5 μm filter. At this time, there was no clogging of the filter. The average particle diameter of the pigment contained in the obtained cyan pigment dispersion was 100 nm, and the viscosity was 19.2 mPa · s. Thus, a good pigment dispersion was obtained only by dispersing the monomer and the resin-treated pigment.

  The average particle diameter and viscosity (viscosity after storage) of the pigment dispersion obtained above after being left at 70 ° C. for 1 week were measured. As a result, the average particle size was 98 nm, and the viscosity was 19.0 mPa · s. As described above, the average particle size of the pigment contained in the pigment dispersion before the test was as fine as about 100 nm, and the initial viscosity was low, but even in the storage stability test, the average particle size was There was almost no change in viscosity and it was very stable.

  Further, as described above, since the resin-treated pigment of the present invention has been previously treated with an AB block copolymer that functions as a pigment dispersant, it is simply added and dispersed in a monomer as a solvent. It was confirmed that it was highly dispersed and maintained high stability.

Next, an ultraviolet curable IJ ink was prepared using the pigment dispersion obtained above with the following composition.
Pigment dispersion 12.5 parts Isobornyl acrylate 44.5 parts 1,6-hexanediol diacrylate 25 parts Trimethylolpropane triacrylate 7 parts Dipentaerythritol hexaacrylate 3 parts Lucyrin TPO (photopolymerization initiator BASF 3 parts Irgacure 819 (manufactured by BASF) 2 parts Irgacure 127 (manufactured by BASF) 3 parts After thoroughly stirring the ink, use a membrane filter with a pore size of 10 μm and then a 5 μm membrane filter. Filtration was performed to obtain IJ ink.

  When the pigment particle diameter in the ink prepared above was measured, it was 98 nm and the viscosity of the ink was 3.7 mPa · s. When the brown sample bottle was loaded with ink and tested for storage stability, the supernatant and sediment were not observed at all. The average particle size of the pigment in the ink after storage was 99 nm and the viscosity was 3.6 mPa.・ It was s. It has been found that by using the resin-treated pigment of the present invention, the pigment adsorbing portion is adsorbed without desorbing from the pigment, and the storage stability of the ink is improved.

Next, the ultraviolet curable IJ ink obtained above was loaded into a cartridge, and solid printing was continuously performed on a polyethylene terephthalate (PET) film for 1 hour using an EB100 inkjet printer manufactured by Konica Minolta. As a result, it was possible to print smoothly without clogging of the head, no streaks or kinks were seen in the solid printing that was the image, and good ejection stability was exhibited even after long-time printing.
As described above, the ink using the resin-treated pigment defined in the present invention has good ejection stability, prints without streaks and kinks even in the case of an ultraviolet curable ink containing many monomers. Confirmed to give things.

  According to the present invention, a resin-treated pigment that is readily useful by treating the pigment with a specific AB block copolymer having a dye molecule in its structure through an ionic bond as defined in the present invention. This resin-treated pigment, when dispersed, exhibits high fine particle dispersibility and high long-term storage stability. In addition to its performance, when used as a color filter colorant, it has high transparency and high Contrast, good alkali developability, and when used as a water-based inkjet ink, it has characteristics that can be applied to various usage methods such as re-dissolvability and ejection stability. Is confirmed, and its wide use is expected. In addition, since the AB block copolymer of the present invention has a dye molecule through an ionic bond in its structure, the resin-treated pigment obtained by treating the pigment using this has a color development property of the pigment to be dispersed. In addition, the coloring property of the pigment present in the polymer is added to further improve the color performance, and there is a possibility that a hue that cannot be achieved by the conventional colorant can be expressed. Moreover, since it is an AB block copolymer having a dye molecule via an ionic bond in its structure, the resin-treated pigment has improved heat resistance and light resistance. Further, the resin-treated pigment provided by the present invention can be used in both aqueous and oily colors, and it can be used for paints, inks, stationery colorants, particularly color filter colorants, UV-IJ colorants, and high-speed printing. Ink-jet ink suitable for the ink-jet printing system can be provided and is expected to be used in various fields.

Claims (3)

A method for producing a resin-treated pigment composition comprising the following AB block copolymer in an amount of 10 to 200 parts per 100 parts of pigment,
In an aqueous solvent having a pigment dispersed with a surfactant having a sulfonic acid group,
An organic dye having in its molecule at least one structural moiety selected from the group consisting of a sulfonic acid, an alkali metal sulfonate, an ammonium sulfonate, and an amine sulfonate ;
A polymer block of A comprising a methacrylate having at least a carboxy group as a constituent component (excluding a case where a methacrylate having an amino group or a quaternary ammonium base is included as a constituent component), and represented by the following general formula (2) An AC block copolymer comprising a C polymer block comprising a quaternary ammonium salt methacrylate as a constituent ;
Reacting either dehydrohalogenated or dehalogenated alkali metal salt or dehalogenated ammonium salt or dehalogenated amine salt ,
The pigment,
One or more sulfonate ions are bonded as a counter ion of a quaternary ammonium nitrogen cation represented by the following general formula (1), which is composed of methacrylate as a structural unit of the A and the structural unit. A process for producing a resin-treated pigment composition , characterized in that the pigment is treated with an AB block copolymer comprising a polymer block of B having an ion-bonding moiety comprising a dye .
[X in Formulas (1) and (2) represents an organic group, and R1 to R3 each independently represents any one selected from the group consisting of a C1 to C18 alkyl group and a benzyl group. D in the formula (1) represents an organic dye molecule, and Y ⁻ in the formula (2) represents a halogen ion. ] Pigment dispersion resin treated pigment composition obtained by the production method of the resin-treated pigment composition according to claim 1, characterized in that the is dispersed. A pigment dispersion liquid, wherein the pigment dispersion according to claim 2 is dispersed in at least one dispersion medium selected from the group consisting of water, an organic solvent, and a polymerizable monomer.