JP2015089906A - Polymer emulsion, coloring agent composition including the same, aqueous inkjet ink, and production method of polymer emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a useful and new emulsion, which is especially suitable for a film forming component of an inkjet ink.SOLUTION: A polymer emulsion is an emulsion of a polymer (a) which has a sulfonic acid ion and in which an emulsion state is stabilized by the sulfonic acid ion and an A-B block copolymer made of a methacrylate monomer corresponding to 90 mass% or more thereof, in which A block has Mn of 1,000-20,000, and a degree of dispersion of 1.5 or less, has a carboxy group, and has an acid value of 30-250 mgKOH/g, where the carboxy group can be neutralized by an alkali, in which B block has a quaternary ammonium ionic group originating from the methacrylate monomer having a quaternary ammonium base, and in which at least a part of counter ions of the sulfonic acid ion of the polymer (a) is the quaternary ammonium ionic group of the B block, and has a bond of ions forming a pair of them.

Description

  The present invention relates to a resin emulsion (polymer emulsion) useful as a film component suitable for printing in an ink jet printing system, a colorant composition comprising the resin emulsion, an aqueous ink jet ink, and a method for producing a polymer emulsion.

  Ink jet printers have been used for various purposes such as personal use, office use, business use, recording use, color display use, and color photography use due to their high functionality. In addition, applications are expanding to support high-speed printing for industrial use. In the water-based pigment ink, in order to improve the sharpness, color tone, color density, etc. of the pigment, the pigment particles in the ink are being miniaturized. On the other hand, in order to cope with higher speed and higher image quality by improving the printer device, the size of ejected droplets (ink droplets) has been reduced. These improvements have resulted in excellent image quality of formed images for inkjet processed paper, especially photographic paper, wide format paper, and the like. However, in recent years, the widespread use of inkjet recording methods has created a need to adapt not only to these papers but also to various paper qualities. There is a problem that the formed image (printed material) is lost.

  For industrial use, printing is performed on large-sized resin films and the like, and in that case, it is necessary to maintain the adhesion of the printed film to the substrate. Depending on the application, there are various types of films, such as polyvinyl chloride, polyolefin, PET, and polystyrene, depending on the application. Adhesive prints are required.

  In order to solve these problems and requirements, it is necessary to add a binder for forming a coating in the ink. There is a need for a binder that achieves high adhesiveness and that has good ink jet printing suitability (high-speed printability and ejection stability). Hereinafter, paper and film may be collectively referred to as a base material.

  On the other hand, the ink may be dried by the recording head of the printing press, etc., and the ink may be dried by the head, and in some cases the color material may solidify. Again, there is a need for redissolvability in which the color material dissolves and disperses in water and returns to the ink.

  For this reason, various binders to be added to the ink have been developed in view of the above-mentioned required performance, and water-soluble polymer solutions such as acrylic, urethane, vinyl, ester, etc., which can be ordinary film components, A solution of the polymer emulsion is added into the ink. However, in the case of a water-soluble polymer, since the polymer is a component that dissolves in the aqueous medium of the aqueous pigment ink, as described below, the viscosity of the ink is increased, making it unsuitable for the ink jet recording system. There was another problem. That is, in the water-soluble polymer, a polymer that exhibits water solubility with an alkali neutralized product of a polymer having a carboxy group may be used, but the following problems arise. In this case, by increasing the carboxy group concentration, the water resolubility becomes higher and the ink re-dissolvability becomes better. On the other hand, since the polymer is dissolved, the ink viscosity tends to increase, In some cases, the ink exhibited non-Newtonian viscosity and could not be ejected well. Furthermore, since there are many carboxy groups, the formed printed film may have poor water resistance.

  Conversely, the following advantages can be obtained by lowering the carboxy group concentration, but the following problems arise. That is, when the concentration of the carboxy group is lowered, the solubility of the resin is lost and particles are formed, resulting in an aqueous dispersion or emulsion, which can lower the viscosity of the ink. Further, the printed film formed because the carboxy group concentration is low. The water resistance is good and the hydrophobicity improves the adhesion to the substrate. On the other hand, the water solubility is poor, so when the ink is dried with a head or the like, it is dissolved and dispersed in the aqueous medium again. This causes a problem that the re-solubility becomes poor. Conventionally, a water-soluble solvent has been used for this problem.

  Examples of aqueous emulsions of polymers include neutralization by adding a small amount of a conventionally known low molecular surfactant, emulsion obtained by emulsion polymerization using a reactive surfactant, or a monomer having a carboxy group. Self-emulsifying emulsions obtained by doing so (see Patent Documents 1-3).

Special table 2003-520279 gazette Japanese Patent Laid-Open No. 2004-197090 JP 2005-179679 A

  However, according to the study by the present inventors, in these conventional techniques, the polymer itself has a high molecular weight and improves the adhesion to the base material. However, when dried, the polymer dissolves in an aqueous medium. In some cases, the redispersibility becomes poor. In addition, the emulsion particle surface is stably emulsified and dispersed in an aqueous medium by a hydrophilicity imparting group such as a surfactant or a copolymer component. However, since the hydration is low, ejection stability may be poor. there were.

  Accordingly, an object of the present invention is to provide an aqueous polymer emulsion that is a new emulsion that can be used as a film component (binder) suitable for an ink jet printing method when applied to ink, which can solve the above-described problems of the prior art. There is to do. Specifically, the object of the present invention is excellent in printability such as high-speed printability and ejection stability in an inkjet printing system, and is particularly useful in the case of an aqueous pigment ink for inkjet using a pigment as a coloring material. It is possible to provide water-based pigment inks for inkjet that are excellent in redispersibility that can be dispersed again even when the ink is dried on the head of a printing press, etc., and that have adhesion to substrates made of various materials. It is to provide a polymer emulsion. Furthermore, another object of the present invention is to provide a simple production method capable of easily obtaining a polymer emulsion having the above excellent properties.

  The above object is achieved by the present invention described below. That is, the present invention relates to a polymer emulsion of a polymer (a) having a sulfonate ion and having an emulsion state stabilized by the sulfonate ion and the following AB block copolymer, the polymer (a) A part or all of the counter ion of the sulfonate ion is composed of an AB block copolymer composed of 90% by mass or more of a methacrylate monomer, and the polymer block of A constituting the AB block copolymer is: The number average molecular weight in terms of polystyrene in the gel permeation chromatography is 1000 to 20000, the dispersity (weight average molecular weight / number average molecular weight) indicating the distribution of the molecular weight is 1.5 or less, and at least a carboxy group is present. And the acid value of the polymer block is 30 to 250 mg KOH / g, The carboxy group in the structure is neutralized with an alkali, and the polymer block of B constituting the AB block copolymer is at least a methacrylate having a quaternary ammonium salt group used as a forming component thereof. A quaternary ammonium ion group derived from a monomer, and at least a part of the counter ion of the sulfonate ion of the polymer (a) is a quaternary ammonium ion group of the polymer block B. Provided is a polymer emulsion characterized in that the polymer (a) and the AB block copolymer have a pair of ionic bonds.

  The following are mentioned as a preferable form of the emulsion of the said invention. That is, the mass ratio of the polymer (a) to the AB block copolymer is 5 to 50:95 to 50; the average particle diameter by light scattering measurement is 20 to 300 nm; the polymer (a ) Is at least one selected from the group consisting of olefin-based, acrylic-based, styrene-based, vinyl alkanoic acid-based, urethane-based and ester-based polymers, or copolymers, graft polymers and block copolymers thereof. And an alkali neutralizing the carboxy group of the polymer block A of the AB block copolymer is ammonia or an organic amine. .

  In another embodiment, the present invention provides a method for producing any of the above polymer emulsions, wherein (I) the sulfonate ion of the polymer (a) having a sulfonate ion is an alkali metal, ammonia or an organic amine. A polymer emulsion (a) which is neutralized with any of the above to form a salt and the emulsified state is stabilized, and an AC block copolymer formed by the following polymer block A and polymer block C: The AC block copolymer is a block copolymer composed of 90% by mass or more of a methacrylate monomer, and the polymer block of A has a polystyrene-reduced number average molecular weight of 1000 to 20000 in gel permeation chromatography, Dispersion indicating molecular weight distribution (weight average molecular weight / number average fraction) Amount) is 1.5 or less, and has at least a carboxy group, the acid value of the polymer block is 30 to 250 mgKOH / g, and the carboxy group in the structure is neutralized with an alkali, Thereafter, the polymer block of C is at least one quaternary ammonium salt selected from the group of halide salts, carbonates, hydroxide salts, and organic carbonate salts. Formed of a monomer containing a methacrylate monomer having a quaternary ammonium ion group constituting (II), and (A) the polymer emulsion (a) by adding the AC block copolymer to the polymer emulsion (a) a) a part or all of counter ions of the sulfonate ion of the polymer (a) in The C polymer block of the A-C block copolymer is subjected to desalting by ion exchange with a quaternary ammonium ionic group constituting the quaternary ammonium salt of the polymer C polymer block of the polymer. Provided is a method for producing a polymer emulsion, characterized in that the polymer block is formed of a polymer block of B having an ionic group, and a polymer emulsion having an ion bond in which a polymer (a) and an AB block copolymer form a pair. .

  The following are mentioned as a preferable form of the manufacturing method of the emulsion of the said invention. That is, in the AC block copolymer, the content of the methacrylate monomer unit having the quaternary ammonium salt is in the range of at least 5 to 50% by mass in the AC block copolymer, and the C In the polymer block of 15 to 100% by mass; the alkali neutralizing the carboxy group in the polymer block of A of the AC block copolymer is ammonia or an organic amine. It is done.

  In addition, the present invention is obtained as another embodiment by at least a dye and / or pigment, water, a water-soluble organic solvent, any one of the above polymer emulsions, or any one of the above production methods. A colorant composition comprising a polymer emulsion is provided.

  Moreover, this invention provides the water-based inkjet ink characterized by containing said colorant composition as another embodiment. As a preferable form, the mass ratio of the polymer which is a constituent component of the polymer emulsion is 50 to 300 parts with respect to 100 parts of the pigment.

  In another embodiment, the present invention relates to a method for producing an AC block copolymer in which 90% by mass or more of the forming component is a methacrylate monomer, which is used in the method for producing a polymer emulsion. A mixture of monomers containing a methacrylic acid-containing monomer is synthesized by living radical polymerization using at least an iodine compound as a polymerization initiating compound to synthesize a polymer block A of an AC block copolymer, and then a quaternary ammonium salt There is provided a method for producing an AC block copolymer, which comprises polymerizing a mixture of monomers including a methacrylate monomer having the following group to synthesize a C polymer block of the AC block copolymer.

  The following are mentioned as a preferable form of the manufacturing method of the AC block copolymer of the said invention. That is, in the living radical polymerization, the amount of the polymerization initiating compound used is such that the total number of moles of monomers forming the polymer block of C is 10 to 150 mol with respect to 1 mol of the polymerization initiating compound; Phosphite compound and phosphinate compound, phosphorus compound; imide compound, nitrogen compound; phenol compound, oxygen compound; diphenylmethane compound, cyclopentadiene compound, hydrocarbon Using at least one selected from the above as a catalyst.

  In another embodiment, the present invention provides a polymer emulsion obtained by using at least a dye and / or pigment, water, a water-soluble organic solvent, and an AC block copolymer obtained by the above production method. A colorant composition characterized by comprising: is provided. Furthermore, the aqueous inkjet ink characterized by including this coloring agent composition is provided.

  According to the present invention, the following excellent effects can be obtained by utilizing the polymer emulsion of the present invention as, for example, a film-forming binder contained in an ink for ink jet recording. First, the adhesion of the printed film to various substrates such as paper or film to which ink is applied can be improved. In the case of the above configuration, since there is no polymer dissolved in the ink and it exists as particles, the viscosity of the ink is low, the ejection stability is improved, and it can be applied to high-speed printing. In addition, even when the ink is dried by the head or the like, re-solubility that is dissolved and dispersed again by a cleaning liquid or the like is added, so that it is possible to provide an aqueous inkjet ink that can stably prevent the occurrence of clogging of the head and the like. It becomes possible. In addition, it is a commercial polymer emulsion that has a track record in various film properties such as adhesion, water resistance, strength, etc. in the market, but it has poor ejection properties for inkjet printing. If so, the technology of the present invention is applied to convert the sulfonate ion constituting the sulfonic acid neutralized salt of the polymer into an AB block copolymer as defined in the present invention. With this, the emulsified state of the polymer can be stabilized. As a result, it is possible to impart high ink jet printing suitability and high dispersion stability to commercially available polymer emulsions that have been used conventionally without changing the physical properties of the films.

  In addition, the AB block copolymer constituting the polymer emulsion of the present invention has unique properties to achieve the above-described remarkable effects of the present invention, but has solved the problems of the conventional living radical polymerization method. It is simple, does not require special compounds, does not require removal of the catalyst after synthesis, can be polymerized under mild conditions, and can be easily obtained with a high yield using a method that does not require special equipment. Therefore, the manufacturing cost can be reduced, and the problem of cost increase due to application to ink can be reduced. In addition, since living radical polymerization carried out to obtain a specific AB block copolymer characterizing the present invention uses a highly safe material, when used as a constituent material of an inkjet ink, Since foreign substances and chemical substances that are not safe are not included, it can be said that the present invention is a technique friendly to the human body and the environment.

  The present invention will be described in detail below with reference to preferred embodiments. As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have found that a polymer emulsion having a sulfonate ion, wherein a part or all of the counter ion of the sulfonate ion is It is possible to solve the above-mentioned problems of the prior art by comprising an AB block copolymer having a characteristic property of, for example, when it is contained as a binder in an ink jet ink The present invention has been found by finding out that the effect can be exhibited. That is, the AB block copolymer characterizing the present invention is composed of 90% by mass or more of a methacrylate monomer. First, the A polymer block of the AB block copolymer has a polystyrene-reduced number average molecular weight in GPC. Is 1000 to 20000, the PDI is 1.5 or less, has at least a carboxy group, the acid value of the polymer block is 30 to 250 mg KOH / g, and the carboxy group in the structure is an alkali It is neutralized or neutralized with an alkali during use. The polymer block B of the AB block copolymer has a quaternary ammonium ion group derived from a methacrylate monomer having a quaternary ammonium salt group used for the polymerization component. The quaternary ammonium ion group becomes a counter ion of a part or all of the sulfonate ion of the polymer (a) constituting the polymer emulsion stabilized with the sulfonate neutralized salt, and the polymer (a) and the AB block A pair of ionic bonds is formed with the copolymer.

  The inventors have already had a polymer block having a carboxy group and a polymer block substantially insoluble in water as a pigment dispersant in a dispersion in which a pigment is finely dispersed in an aqueous medium. By using block copolymer, it has high microdispersibility, high storage stability, and high re-dissolvability to disperse again in a liquid medium even after drying, high ejection stability, long run printing suitability, etc. Suitable pigment dispersions have been developed (eg PCT / JP2009 / 063265). This is because the carboxy group in this block copolymer is neutralized with an alkali, so it can be dissolved in an aqueous medium, which is the dispersion medium of the dispersion liquid, resulting in fine dispersion and high stability of the pigment due to steric repulsion and steric hindrance. In addition, because of its high hydrophilicity, even when dried, the polymer block dissolves in water and can be redispersed. In addition, since this block copolymer has a polymer block insoluble in water, and there is no polymer dissolved in the dispersion, it is uniform in viscosity, so the viscosity of the ink containing it is constant. , Suitable for discharge stability and long run printing. That is, the outline of the previously proposed technique is that the block copolymer having the above-mentioned specific configuration is used as a pigment dispersant, whereby the pigment is encapsulated with a water-insoluble polymer block, and the water-soluble polymer block is converted into water. It has been achieved by dissolving and obtaining this excellent action.

  On the other hand, as described above, the conventional emulsion used as a binder component in the ink lacks ejection stability when the ink is contained in the ink, or the re-dissolvability of the dried ink is poor. was there. With regard to these causes, the present inventors have found that conventional emulsions only have a hydrophilic property on the surface of the emulsion particles that contributes to the stability of the emulsion particles, and are insufficient in mechanical stability in water and sufficient hydrophilicity. I thought it was not. Then, the present inventors utilize the concept of pigment dispersibility in the above-described pigment dispersant, so that the surface of the polymer emulsion particles is bonded to and coated with the polymer emulsion particles, and the polymer that dissolves in water. It came to be thought that by modifying the surface with the block, it was possible to impart re-dissolvability of dried ink, ink ejection stability, and long-run printability, which could not be achieved by conventional emulsions.

  Therefore, the present inventors have conventionally become a counter ion of a sulfonate ion constituting the sulfonate group in a polymer emulsion stabilized with a sulfonate neutralized salt used in inkjet inks. A polymer block having a quaternary ammonium salt in the form of a quaternary ammonium ion that is a counter ion of the sulfonate ion in a polymer emulsion. On the other hand, it has been concluded that it is effective to use a block copolymer having a carboxy group and having a polymer block having a property of being neutralized, ionized and dissolved in water. That is, the present inventors can utilize the block copolymer having such properties to modify the block copolymer stabilized with a sulfonate salt conventionally used in ink as a binder component. The quaternary ammonium salt becomes a counter ion of the polymer sulfonate ion of the polymer emulsion and binds to the polymer particles of the polymer emulsion, and the other water-soluble polymer block constituting the block copolymer is in water. It was considered that by dissolving, the layer to be re-dissolved and hydrated was enlarged, and the ejection stability was improved. As a result of intensive studies under such recognition, the present inventors have found a polymer emulsion of the present invention having the following constitution that can provide a remarkable effect, and have reached the present invention.

  That is, the remarkable effect of the present invention can be obtained for the first time by using a polymer emulsion having the following constitution. The polymer emulsion of the present invention is basically formed by using, as a raw material, an emulsion stabilized with a sulfonic acid neutralized salt conventionally used as a binder component of an ink. As described above, the portion stabilized by the sulfonate is modified so that a part or all of the counter ion of the sulfonate ion is an AB block copolymer having a specific configuration. is there. Specifically, the emulsion of the present invention is a polymer emulsion having a sulfonate ion, and a part or all of the counter ions of the sulfonate ion of the polymer constituting the emulsion is 90% by mass or more of methacrylate. It is obtained for the first time by using the following specific AB block copolymer consisting of a monomer. The AB block copolymer is a polymer block of A having a polystyrene-reduced number average molecular weight in GPC (hereinafter, the number average molecular weight may be referred to as Mn) of 1000 to 20000, and its PDI Is 1.5 or less, and has at least a carboxy group, the acid value of the polymer block of A is 30 to 250 mg KOH / g, and the carboxy group in the structure is finally used in use. The polymer block of B is at least neutralized with an alkali, and has at least a structural unit composed of a methacrylate monomer having a quaternary ammonium group. As a result, in the polymer emulsion, the sulfone The counter ion of the acid ion is a quaternary ammonia of the B polymer block of the AB block copolymer. Become a thing of the configurations are-ion.

  The polymer emulsion of the present invention having such a specific constitution can be easily obtained by the following method of the present invention. That is, the polymer emulsion (a), which has been conventionally known and is stabilized as a salt by neutralization with an alkali metal, ammonia, or an organic amine, is converted into a methacrylate-based polymer of 90% by mass or more as described below. It is easily obtained by adding the following specific AC block copolymer consisting of monomers. That is, the AC block copolymer used for this addition has an A polymer block that becomes an A polymer block of the AB block copolymer that is a counter ion of the sulfonate ion, and the C polymer block is, for example, A-C having such a structure is composed of a polymerization component having at least a methacrylate monomer having a quaternary ammonium ion group having a salt structure such as a halide salt, a carbonate salt, a hydroxide salt, or an organic carbonate salt. By adding the block copolymer, part or all of the sulfonic acid counter ion of the polymer of the polymer emulsion (a) is exchanged with the quaternary ammonium ion group of the C polymer block of the AC block copolymer. The counter ion of the sulfonate ion in the polymer emulsion is AB bromine. It becomes Kukoporima, it is possible to obtain a polymer emulsion of the present invention.

  The polymer particles that characterize the polymer emulsion of the present invention have the above-described configuration, and the sulfonate ion counter ion is the above-described unique AB block copolymer having a quaternary ammonium ion group, so that it is soluble in water. Therefore, when this is used as a constituent component of the ink-jet ink, problems such as changes in the viscosity of the ink and lack of ejection stability do not occur. On the other hand, the polymer block A of the above-mentioned unique AB block copolymer has a carboxy group neutralized with an alkali, so it has high solubility in water, and even if the ink is dried by the head, It is easy to dissolve in a liquid medium such as an alkaline aqueous solution (that is, good resolvability), and the ink can be excellent in resolubility. Furthermore, since the polymer of the polymer emulsion of the present invention has a very large molecular weight as compared with the conventional polymer because the counter ion is a specific AB block copolymer, as a result, film formation such as ink jet ink is performed. A good film having high toughness and high adhesion, useful as a component, can be obtained. Since the emulsion of the present invention has unique properties as described above, it can be solved at once by applying it to the binder component of inkjet ink.

  Living radical polymerization is suitable as a method for obtaining an AC block copolymer having a specific structure necessary for realizing the emulsion composition of the present invention. Hereinafter, this point will be described. First, there are various methods for living radical polymerization. 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. However, as described below, each method has its own problems, and it is difficult to say that it is an optimum method for obtaining an AC block copolymer having the properties required in the present invention. That is, the NMP method requires a high temperature, and the polymerization of the methacrylate monomer cannot be performed well by living polymerization. In addition, atom transfer radical polymerization uses the metal complex, and the metal complex uses an amine compound as a ligand. Therefore, a monomer having a carboxyl group cannot be polymerized as it is. Further, reversible addition-cleavage type chain transfer polymerization has a problem that it has an odor because it uses a sulfur compound.

  According to the study by the present inventors, the AC block copolymer having the specific properties necessary for obtaining the AB block copolymer characterizing the present invention can be easily produced by the following living radical polymerization. can get. Specifically, in conventional radical polymerization, it is produced by living radical polymerization using an iodine compound as a polymerization initiating compound and, if necessary, an organic compound having active phosphorus, nitrogen, oxygen and carbon atoms as a catalyst. It is preferable to do. By producing in this way, a polymer having a narrow PDI, that is, a uniform molecular weight can be easily obtained. Since the polymer has this narrow molecular weight distribution, there are no polymer molecules that are easily dissolved in water and polymer molecules that are difficult to dissolve in water, and the properties are uniform. On the other hand, a polymer emulsion having a property that is very stable can be obtained by having a polymer block that always dissolves in water, and the polymer emulsion of the present invention using this as a binder component. When used, it is possible to obtain the optimum performance for the discharge property of the ink jet printing method.

Next, the present invention will be described in detail by giving preferred embodiments of the emulsion of the present invention.
The present invention relates to a polymer emulsion, and the polymers contained therein are composed of the following two types. Specifically, it is composed of a polymer in which the water-emulsification stability imparting group of the polymer is a sulfonate ion and an AB block copolymer that is a part or all of the counter ion of the sulfonate ion. . The AB block copolymer has a quaternary ammonium ion group as a counter ion in one polymer block, and the other polymer block has a neutralized carboxy group. The emulsion is stably emulsified and dispersed in water with the AB block copolymer having this specific property. The polymer stabilized by the AB block copolymer includes an AC block copolymer prepared for forming a counter ion and a polymer stabilized by a sulfonate ion that has been conventionally used. It is obtained by salt exchange (ion exchange) with a polymer of emulsion (a) (hereinafter sometimes referred to as emulsion (a)). The term “salt exchange” as used in the present invention refers to a quaternary ammonium salt in which the C polymer block of the AC block copolymer has a counter ion of the sulfonate ion of the polymer emulsion stabilized with the sulfonic acid neutralized salt. Means that it is replaced with a quaternary ammonium ion derived from This ion replacement is performed by a part or all of the sulfonate ions.

  The polymer block of A-C prepared for the counter ion of the sulfonate ion is such that the polymer block of A has a polystyrene-equivalent number average molecular weight of 1000 to 20000 and a PDI of 1.5 or less. And having at least a carboxy group, the acid value of the polymer block being 30 to 250 mgKOH / g, and the carboxy group in the structure being neutralized with an alkali or neutralized at the time of use The polymer block of C is a quaternary ammonium ion constituting at least a quaternary ammonium salt of a halide salt, carbonate, hydroxide salt, or organic carbonate salt as a structural unit. It is a polymer composed of a methacrylate monomer having a group. The polymer emulsion (a) constituting the present invention, which is a raw material modified by the AC block copolymer, is a polymer emulsion whose emulsified state is stabilized with a sulfonic acid neutralized salt. Hereinafter, each of these materials will be described.

[AC block copolymer]
First, the AC block copolymer will be described. This AC block copolymer, as described above, is a polymer component that becomes the counter ion of the sulfonate ion of the polymer stabilized with the sulfonate salt, whereby the stability of the polymer emulsion particles of the present invention, Functions such as re-solubility and ejection stability are added. That is, the polymer emulsion of the present invention has a unique block copolymer having a carboxy group neutralized in the structure of the sulfonate ion counter ion of the polymer particles constituting the emulsion. It is modified to have a remarkable effect. The counter ion of the sulfonate ion is a quaternary ammonium ion constituting a quaternary ammonium salt contained in the C polymer block of the AC block copolymer, whereby the polymer in which the block copolymer constitutes an emulsion. Combined with particles. That is, in the present invention, polymer particles of a polymer emulsion stabilized with a sulfonate salt are divided into a polymer block of A having a water-soluble carboxy group and a polymer block of C having a quaternary ammonium salt group. It is characterized by using a structured AC block copolymer and modifying it by ionic bonding.

  According to the study by the present inventors, in contrast to this, carboxy groups and quaternary ammonium salts are randomly selected as a material for modifying the polymer particles of the polymer emulsion stabilized with the sulfonate. When using a random copolymer obtained by conventional radical polymerization which is arranged, the quaternary ammonium salt is randomly in the polymer chain, so that the whole polymer is ion-exchanged with the sulfonic acid of the polymer particles of the emulsion (a). In this case, unlike the block copolymer that characterizes the present invention, there is no polymer chain that dissolves in water, and thus the agglomeration occurs. On the other hand, as described above, in the present invention, the quaternary ammonium salt is concentrated on one polymer block to make it into a specific molar range (molecular weight range), thereby preventing the particles from aggregating with each other. The sulfonate portion of the polymer particles contained in (a) is treated with this AC block copolymer to replace ions to form an AB block copolymer to form an ion pair bond. Makes the polymer emulsion of the present invention useful. The polymer block of A that constitutes the AB block copolymer that characterizes the present invention has a neutralized carboxy group in the state in which it is used, and thus works very effectively in ejection stability and re-solubility. .

  The AC block copolymer used to form the AB block copolymer characterizing the polymer emulsion of the present invention described above is an AC block copolymer composed of 90% by mass or more of a methacrylate monomer, It consists of two types of polymer blocks. First, the polymer block of A has a polystyrene-equivalent number average molecular weight of 1,000 to 20,000 in GPC, its PDI is 1.5 or less, has at least a carboxy group, and has an acid value of 30 to 30. It is 250 mgKOH / g, and the carboxy group in the structure is neutralized with an alkali or subsequently neutralized. The polymer block of C is a polymer comprising at least a methacrylate monomer having a quaternary ammonium salt group such as a halide salt, carbonate, hydroxide salt, or organic carbonate salt as a forming component. It is.

  The AC block copolymer used in 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 AC 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 monomer other than the methacrylate monomer is used in a large amount, there is a possibility that problems such as not having a specific structure intended in the present invention or spreading of PDI 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)
Although the main component of the AC block copolymer is a methacrylate monomer, the polymer block of A is required to have at least a carboxy group. For example, a carboxy group-containing methacrylic acid type as described below If a polymer block of A is formed using a monomer, a polymer block of A containing a structural unit having a carboxy group derived from the monomer in the structure can be easily obtained. Furthermore, the polymer block of A having a carboxy group introduced into the structure used in the present invention is ionized and dissolved in water when the carboxy group is neutralized with an alkali. For this reason, the AC block copolymer used in the present invention dissolves in an aqueous medium, stabilizes the polymer particles by steric repulsion and steric hindrance, and further has a neutralized carboxy group. Even if it dissolves again with an aqueous medium, re-solubility is imparted.

  Specific examples of the carboxy group-containing methacrylic acid 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 an AC block copolymer, a monomer having a carboxy group in the polymer block of A is not used as a constituent component, and a block copolymer is obtained by polymerizing glycidyl methacrylate as at least a constituent component. A compound having a carboxy group, 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 reacting an acid or the like to form an AC block copolymer composed of the same A polymer block as that formed with the carboxy group-containing methacrylic acid monomer listed above. Forms are also included in the present invention. In addition, although it is not preferable because the number of steps increases, it is not preferable to use a monomer in which carboxylic acid of methacrylic acid is protected, such as t-butyl methacrylate, trimethylsilyl methacrylate, methacrylic acid protected by hemiacetalization by reacting with vinyl ether. After the polymerization, a block copolymer may be synthesized and deprotected to form a carboxy group to be a polymer block of A. As described above, in the present invention, it is preferable to use a carboxy group-containing methacrylic acid monomer, and more preferably, the polymer block of A may be formed using methacrylic acid. That is, since methacrylic acid has the smallest molecular weight, even if the introduction amount is small, sufficient water solubility can be imparted and there is no hydrolyzability. Hereinafter, the method for forming the polymer block of A may be described using a typical carboxy group-containing methacrylic acid monomer as an example, but as described above, a carboxy group is introduced into the polymer block of A. The method to do is not limited to this.

  In the above case, the polymer block of A may be formed only with a carboxy group-containing methacrylic acid monomer, but it is a preferred form to copolymerize other copolymerizable methacrylates. By copolymerizing with these monomers, the acid value required by the present invention can be easily adjusted. As another monomer component, a conventionally well-known methacrylate can be used and it does not specifically limit. 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 methacrylate in which the isocyanate group of 2- (2-isocyanatoethoxy) ethyl methacrylate is blocked with ε-caprolactone, MEK oxime, and pyrazole; cyclic such as tetrahydrofurfuryl methacrylate 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 also be used.

  However, methacrylate having an amino group or a quaternary ammonium base must not be used for the methacrylate monomer forming the A polymer block constituting the AC block copolymer used in the present invention. That is, in the present invention, the methacrylate having an amino group or a quaternary ammonium base is introduced only into the constituent component of the C polymer block. The reason for this is that when a methacrylate having an amino group or a quaternary ammonium base is used as the component for forming the polymer block of A, the A-C block copolymer used in the present invention is constituted in order to obtain the polymer emulsion of the present invention. It is necessary to selectively exchange the polymer block of C with the sulfonate ion of the polymer particles of the emulsion (a). When an amino group or a quaternary ammonium salt is contained in the polymer block of A, This is because the polymer block also reacts with the sulfonate ions of the polymer particles of the emulsion (a) and cannot be made into the polymer emulsion of the present invention.

  The polymer block of A of the AC block copolymer used in the present invention needs to have an acid value of 30 to 250 mgKOH / g. Furthermore, it is preferable that it is 50-200 mgKOH / g. When the acid value of the polymer block of A is less than 30 mgKOH / g, sufficient water solubility cannot be obtained and stability may be inferior. On the other hand, when the acid value of the polymer block of A exceeds 250 mgKOH / g, the water solubility of the polymer block of A is too high, and thus the polymer emulsion of the present invention was used as a binder component of the ink. In such a case, the viscosity of the ink may increase or the water resistance of the formed printed film may be inferior. The acid value is the number of mg of potassium hydroxide required to neutralize 1 g of the resin, and the measurement is a resin dissolved in an organic solvent (for example, toluene / ethanol = 70/30 mass ratio). Can be carried out by titrating 0.1N potassium hydroxide as a titrant and phenolphthalein as an indicator. In the present invention, this value is used for the acid value.

  The polymer block of A of the AC block copolymer used in the present invention needs to have a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000 in gel permeation chromatography (GPC). More preferably, it is 4000-15000. If the number average molecular weight of the polymer block of A is less than 1000, 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, the molecular weight is small. If it is too high, the solubility and compatibility may be poor. On the other hand, when the number average molecular weight of the polymer block of A exceeds 20000, the portion that dissolves or is compatible with the dispersion medium increases, and therefore the viscosity may increase excessively.

  The polymer block A in the AC block copolymer used in the present invention requires a molecular weight distribution (weight average molecular weight / number average molecular weight, PDI) of 1.5 or less, but 1.4 or less. Is more preferable. According to the method for producing an AC block copolymer, which will be described later, an AC block copolymer having a narrow molecular weight distribution as described above can be suitably produced according to the design. If the PDI of the polymer block of A exceeds 1.5, the number average molecular weight will be less than 1000 or more than 20000 will be included, so its stability will decrease and viscosity will increase excessively It is not preferable because there is a risk of doing so. 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 AC block copolymer used in the present invention.

(C polymer block)
Next, the C polymer block constituting the AC block copolymer used in the present invention will be described. The polymer block of C is a polymer block having at least a constituent unit composed of a methacrylate monomer having a quaternary ammonium salt group such as a halide salt, carbonate, hydroxide salt or organic carbonate salt.

  The methacrylate monomer having a quaternary ammonium salt group is a methacrylate having a quaternary ammonium ion group having a counter ion as an anion of halide, hydroxide, carbonic acid, or organic carbonate. As described above, the above counter ion undergoes salt exchange (ion exchange) with the sulfonic acid neutralized salt counter ion of the polymer emulsion (a) stabilized with the sulfonate, As a result, the sulfonic acid ion of the polymer of the emulsion (a) is bonded to the sulfonate portion of the polymer of the emulsion (a) by the reaction of the AC block copolymer used in the present invention with an ionic bond. Part or all of the counter ion becomes an AB block copolymer. Below, the counter ion of the methacrylate of the quaternary ammonium salt mentioned above is demonstrated. Examples of halide ions include chloride ions, bromide ions, and iodide ions. Among them, chloride ions are preferable. That is, in the case of bromide ions and iodide ions, the basicity thereof is strong and there is a possibility that the exchange reaction with the sulfonate is not performed. Examples of the organic carbonate ions include methyl carbonate ions and ethyl carbonate ions. As a result, decarboxylation and dealcoholization react with the sulfonic acid neutralized salt. In particular, methyl carbonate ions are preferable because decarboxylation and methanol, which is a lower alcohol, are produced.

  Specific examples of the methacrylate containing a quaternary ammonium salt group include, for example, methacrylate esters of mono- or dialkylaminoalkyl alcohols such as dimethylamino methacrylate, diethylaminoethyl methacrylate, and t-butylaminoethyl methacrylate, and glycidyl methacrylate. Using an amino group-containing methacrylate having a hydroxyl group obtained by reacting a glycidyl group-containing methacrylate with an amine compound having a primary or secondary amino group, methyl chloride, ethyl chloride, benzyl chloride, methyl iodide, etc. And methacrylates having a quaternary ammonium salt group obtained by reacting alkyl halides of carbonic acid, carbonic acid and dimethyl carbonate, and quaternary ammonium salts in which their anions are replaced with hydroxides.Or, a methacrylate having a halogenated alkyl group, such as 2-chloroethyl methacrylate, 1-chloro-2-hydroxypropyl methacrylate, or the like, an amine compound having a primary, secondary, or tertiary amino group, such as trimethylamine May be converted to a quaternary ammonium salt. It is essential to use these quaternary ammonium salts as components for forming the polymer block of C. As mentioned earlier, the above-mentioned monomers should never be used to form the polymer block of A, that is, the quaternary ammonium salt group should not be introduced into the polymer block of A.

  The polymer block of C may be composed of only the methacrylate having the quaternary ammonium salt group, but may be copolymerized with other methacrylate monomers as listed above. The content of the group of the quaternary ammonium salt is contained in the AC block copolymer used in the present invention in a range of at least 5 to 50% by mass, and 15 to 100 in the polymer block of C. It is preferable that it is contained in a mass% range. Other methacrylate monomers can be copolymerized in this range. Examples of the methacrylate used in this case include those described above, and are not particularly limited. For the C polymer block, the monomer having a carboxy group described above may be used as a constituent component. The reason for this is that even when this carboxy group is neutralized, the quaternary ammonium salt moiety introduced into the structure is subjected to salt exchange (ion exchange) with the counter ion of the sulfonate ion as described above. ) There is no problem because it reacts with the polymer particles of the emulsion (a). That is, in the present invention, only the C polymer block constituting the AC block copolymer used in the present invention (that is, only one polymer block) contains a quaternary ammonium salt group. is necessary.

  When the content of this quaternary ammonium salt in the A-C block copolymer is less than 5% by mass in the A-C block copolymer, there are few reactive sites with the sulfonic acid group of the polymer and the stability is lacking. In addition, when the amount is more than 50% by mass, the polymer block of A is relatively too small, which may be inferior in dispersibility and dispersion stability. More preferably, it is 10-50 mass%. Furthermore, while maintaining the amount of the quaternary ammonium salt contained in the AC block copolymer within the above-mentioned range, the mass of the quaternary ammonium salt monomer contained in the polymer block of C is 15 to 100% by mass. It is preferable to do. If this amount is less than 15%, there are few reactive sites in the polymer block of C, and there are many other components even if it reacts with sulfonate ions, so it dissolves in the dispersion medium and is dispersed and storage stable. This is not preferable because the property may deteriorate. More preferably, it is 20-80 mass%.

(Preparation of AC block copolymer)
It is difficult to obtain the AC block copolymer used in the present invention having a specific structure composed of the components as described above (formation) by ordinary radical polymerization. That is, radical polymerization results in the random copolymer described above or a mixture of a copolymer having a carboxy group and a copolymer having a quaternary ammonium salt. On the other hand, the polymer emulsion of the present invention is premised on obtaining an AC block copolymer having the above structure defined in the present invention. According to the study by the present inventors, the AC block copolymer defined in the present invention can be easily obtained by living radical polymerization. Particularly preferably, a polymer block of A of the AC block copolymer is synthesized by subjecting a mixture of monomers including at least a carboxy group-containing methacrylic acid monomer to living radical polymerization using at least an iodine compound as a polymerization initiating compound, Then, a monomer mixture containing a methacrylate monomer having a quaternary ammonium salt group is polymerized to produce a polymer block of C of the A-C block copolymer by a production method using a unique living radical polymerization. A C block copolymer may be obtained. More specifically, the polymerization initiating compound used in the step of living radical polymerization in the presence of the polymerization initiating compound and the catalyst is at least one of iodine or an iodine compound, and the catalyst used in the step is It is at least one compound selected from the group consisting of phosphorus halides, phosphite compounds, phosphinate compounds, imide compounds, phenol compounds, diphenylmethane compounds and cyclopentadiene compounds, and its polymerization temperature. Is preferably 30 to 50 ° C.

  Various methods have been invented for living radical polymerization, such as nitroxide mediated polymerization (NMP method) using dissociation and bonding of amine oxide radicals, heavy metals such as copper, ruthenium, nickel, iron, and the like. Atom transfer radical polymerization (ATRP method) in which a heavy metal and a ligand that forms a complex are used as a starting compound, and a dithiocarboxylic acid ester or a xanthate compound is used as the starting compound. In addition, reversible addition-fragmentation chain transfer polymerization (RAFT method) and MADIX method (Macromolecular Design via Interchange of Xanthate), organic tellurium, polymerizing using addition polymerizable monomer and radical initiator, Organic bismuth, organic antimony, halo Down antimony, 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, any of the above-mentioned methods has a problem that it is difficult to say that it is optimal for obtaining the AC block copolymer used in 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 oxidation and reduction, it is necessary to remove oxygen. 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 suitably 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 a comparison in the market. Therefore, it can be easily manufactured only by using inexpensive materials. 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 AC block copolymer used in the present invention includes a step (polymerization step) of subjecting a monomer component containing a methacrylate monomer to living radical polymerization in the presence of a polymerization initiating compound and a catalyst. It is preferable. The polymerization initiating compound is preferably 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, it is preferable to polymerize a monomer component containing a methacrylate monomer by living radical polymerization using at least one of iodine and an iodine compound as a polymerization initiating compound. 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. In addition, an organic halide obtained by substituting iodine of the above iodine compound with a halogen atom such as bromine or chlorine is reacted with an iodide salt such as quaternary ammonium iodide or sodium iodide, and the halogen compound is exchanged. 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. Catalysts include phosphorus compounds such as phosphorus halides, phosphite compounds, 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 polymerizations 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.

The AC block copolymer used in the present invention is one in which the molecular weight of the main chain is controlled by adjusting the use balance of methacrylate monomers and polymerization initiating compounds at the time of living radical polymerization. Become. 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, the AC block copolymer used in the present invention having a specific structure is produced 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.

  In addition, as the order of block polymerization of the AC block copolymer used in the present invention, a polymer block of A is formed using a carboxy group-containing methacrylic acid monomer, and then a quaternary ammonium salt is included. A methacrylate polymer block may be added to form a polymer block of C, or a methacrylate having an amino group or a methacrylate having an alkyl halide to form a quaternary ammonium salt may be added and polymerized to form a block copolymer. Then, quaternary ammonium chloride may be used to form an AC block copolymer.

  Alternatively, after polymerizing a methacrylate containing a methacrylate containing a quaternary ammonium base, a monomer for forming a polymer block of A may be added and polymerized, or an amino group-containing methacrylate or alkyl halide may be added. The monomer containing the methacrylate may be polymerized to form a polymer block, and then the component for forming the polymer block of A may be polymerized, followed by quaternary ammonium chloride. However, in these methods, a monomer containing a quaternary ammonium salt, an amino group or an alkyl halide is polymerized until it is completely removed, or the monomer is removed by purification to remove the next polymer block. It is necessary to form. When a monomer having a quaternary ammonium salt, an amino group, or an alkyl halide is introduced into the subsequent polymer block formation of A, the entire block copolymer becomes a polymer that reacts with sulfonate ions, This is because only one of the present invention cannot be a block copolymer containing a quaternary ammonium base.

  More preferably, in order to ensure that one polymer block has a quaternary ammonium base, after forming a polymer block of A using a carboxy group-containing methacrylic monomer, a quaternary ammonium salt, It is certain to block monomers having amino groups and alkyl halides. In addition, as mentioned above, there is no problem even if the carboxy group-containing methacrylic acid monomer is used as a constituent component in the polymer block of C.

  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, or it is preferable to desorb iodine atoms. The method for desorbing iodine atoms from the AC block copolymer is not particularly limited as long as it is a conventionally known method. Specifically, the AC block copolymer may be heated or treated with an acid or alkali. Further, the AC 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.

  Next, the molecular weight of the AC block copolymer will be described. The molecular weight of the polymer block A constituting the AC block copolymer used in the present invention is as described above. The preferred molecular weight of the polymer block A is as described above. The number average molecular weight of the whole of these block copolymers is not particularly limited, but is a molecular weight obtained in the range of the content of the polymer block of C described above. However, the number average molecular weight of the AC block copolymer used in the present invention cannot be accurately measured by a conventionally known GPC. The reason is that when the AC block copolymer used in the present invention is amphoteric and has a carboxy group and a quaternary ammonium salt, GPC equipped with a column to which the carboxy group does not adsorb is used. When the measurement is performed with a column capable of measuring the quaternary ammonium salt because the quaternary ammonium salt is adsorbed, the polymer having a carboxy group is adsorbed and cannot be measured. In some cases, an accurate molecular weight cannot be obtained. That is, it is possible to measure only the polymer block of A before making it an AC block copolymer.

  Therefore, since the molecular weight cannot be defined as described above, the following limitation is made so that the molecular weight of C can be defined. In the present invention, it is preferable to use a specific living radical polymerization method for the production of the AC block copolymer. As described above, in this living radical polymerization, a polymerization initiating compound having a group that is easily dissociated as a radical is generally used. 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, preferably, this living radical polymerization is used for the production of the AC block copolymer used in the present invention, and the radical polymerization property comprising the polymerization initiating compound and the monomers used for the polymerization. Although the methacrylate which is the group is used, the amount of methacrylate constituting the polymer block of A is adjusted so that the polymer block of A has the above-described molecular weight. However, since the molecular weight of the polymer block of C 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 monomers forming the C polymer block is preferably 10 to 150 mol with respect to 1 mol of the polymerization initiating compound. The amount of the C polymer block is adjusted within this range, and is adjusted together with the mass% of the quaternary ammonium salt contained in the C polymer block. If the amount is less than 10 mol, the molecular weight of the polymer block of B becomes too small, and the effects of the present invention cannot be sufficiently exerted. This is not preferable because it may cause aggregation and aggregation. Preferably, it is 20 mol to 100 mol with respect to 1 mol of the starting compound of B.

  The polymer emulsion of the present invention is a polymer emulsion particle in which the polymer block of C constituting the AC block copolymer used in the present invention is stabilized in an emulsified state with a sulfonic acid neutralized salt. It becomes a counter ion, and the carboxy group of one A polymer block is neutralized with an alkali and dissolved in water. As the alkali, conventionally known alkalis are used, and ammonia and organic amines are particularly preferable. Specific examples include ammonia, trimethylamine, ethanolamine, diethanolamine, triethanolamine, tripropanolamine, morpholine, N-methylmorpholine, 2-amino-2-methyl-1-propanolamine and the like. Although alkali metals such as sodium hydroxide and potassium hydroxide can be used, it is not preferred. The reason for this is achieved in the present invention by ionization of the sulfonate of the polymer emulsion particles and the quaternary ammonium salt of the AC block copolymer. When a strong alkali such as sodium hydroxide enters here, the reason is as follows. This is because the quaternary ammonium salt and the sulfonic acid salt may be substituted with sodium ions to form a sulfonic acid sodium salt, which may not form the counter ion of the present invention. Further, the AC block copolymer used in the present invention is used by neutralizing 60 mol% or more, preferably 100% or more, of the carboxy group of the polymer block of A to make it an aqueous solution. Cost.

  The AC block copolymer used in the present invention can be obtained by solution polymerization. However, the carboxy group of the polymer block A may be neutralized by adding an alkali as it is, or once precipitated in a poor solvent. Alternatively, the polymerization solvent may be removed and taken out as a solid, neutralized with an alkali, and used as an aqueous solution. Furthermore, it can be used as it is as follows. Since the AC block copolymer used in the present invention is a block copolymer having a quaternary ammonium salt group, the polymer block of C becomes a polymer block that dissolves in water, and the polymer solution obtained by solution polymerization is directly used in water. When diluted, since the polymer block of A is not neutralized, it does not dissolve in water, but can be converted into particles as a dispersion or emulsion to form an aqueous solution. In this case, as will be described later, an alkali capable of neutralizing the polymer block of A is previously added to the polymer emulsion solution (a) stabilized with the sulfonate salt to be modified with the AC block copolymer. Thus, when the AC block copolymer solution or the solution diluted with water is added, the polymer block of A can be neutralized.

  When the polymerization solution is neutralized and used as a solution, the polymerization solvent is preferably an organic solvent that is at least partially soluble in water. This is because if it is insoluble in water, it may not be mixed with the polymer emulsion (a). More preferably, it is an organic solvent that dissolves completely, and is suitably used from the above-mentioned solvents, and is not particularly limited. Preferred are solvents in alcohols, glycols, ethers and amides.

  An AC block copolymer can be obtained as described above. The polymer emulsion of the present invention is a polymer sulfonate salt stabilized with the sulfonate salt of the polymer emulsion (a) to be modified, the quaternary ammonium salt of the AC block copolymer used in the present invention. The counter ion of the sulfonate salt of the polymer particles of the polymer emulsion (a) is a quaternary ammonium ion derived from an AC block copolymer. Next, the polymer emulsion (a) will be described.

[About polymer emulsion (a)]
As described above, the polymer emulsion (a) used as a raw material in the present invention is a dispersed and emulsified polymer emulsion having polymer particles whose emulsion state is stabilized with a sulfonic acid neutralized salt. The emulsion stabilized with the sulfonate group is a conventionally known polymer emulsion, and the sulfonic acid is a polymer emulsion (a) neutralized with an ammonium salt, an organic amine salt or an alkali metal salt. The counter ion for neutralization is not particularly limited. Although there are polymer emulsions in which the emulsified state is stabilized with phosphates or the like, according to the study by the present inventors, a structure in which a polymer emulsion stabilized with sulfonates is used as a raw material and this is modified. In this case, the effect of the present invention can be obtained more remarkably.

  This polymer emulsion (a) stabilized with sulfonic acid groups (hereinafter also simply referred to as polymer emulsion (a)) uses a surfactant having a sulfonate salt or copolymerizes a monomer having a sulfonic acid group. Or obtained in combination. The surfactant and the monomer having a sulfonic acid group are not particularly limited, and the content thereof is not limited. When a surfactant is used, it can be obtained by emulsion polymerization or polymerization using an organic solvent, which is a solvent evaporation method, and adding an activator and water to emulsify and remove the solvent. In the case of a copolymer of monomers having a sulfonic acid group, it becomes a self-emulsifying polymer and is emulsified. These methods are not particularly limited.

  As the polymer emulsion (a), conventionally known ones are used. In the present invention, olefin-based, acrylic-based, styrene-based, vinyl alkanoate-based, urethane-based, ester-based polymers, and copolymers thereof are particularly used. At least one of a polymer, a graft polymer and a block copolymer is used. These serve as a coating component when applied or printed as a binder component, and serve as adhesion to the substrate, protection of the substrate, and the like.

  First, an olefin type, an acrylic type, a styrene type, and a vinyl alkanoate type will be described. These production methods are not particularly limited, and can be obtained, for example, by emulsion polymerization using the above-described surfactant, solvent evaporation, self-emulsification by copolymerization of a sulfonic acid group-containing monomer, or a combination thereof. The surfactant is not particularly limited as long as it is a surfactant having a sulfonate, and examples thereof include dodecylphenylsulfonic acid, naphthalene formaldehyde condensate sulfonated product, dodecylsulfonic acid, dodecylphenyl polyethylene glycol monosulfonic acid, octyl. Alkali metal salts, ammonium salts, organic amine salts and the like of sulfonated products such as sulfosuccinic acid, sulfosuccinic acid alkyl ester, and polyoxyalkylene alkenyl ether ammonium sulfate can be used.

  Further, as the polymer activator, a polymer type activator obtained by polymerizing a monomer containing a sulfonate and another monomer can also be used. The above olefin-based polymer monomers have unsaturated bonds, so they can be obtained by radical polymerization. However, with the above low-molecular-weight surfactants, bubbles are generated due to the presence of low-molecular-weight surfactants in the aqueous system. Therefore, the emulsion can be obtained by using a reactive surfactant having a radical polymerizable group and using a sulfonic acid group as a copolymerization component. As this reactive surfactant, conventionally known surfactants are used, and the amount used is not particularly limited. For example, ethyl methacrylate sulfonic acid, polyethylene glycol methacrylate methacrylate, styrene sulfonic acid, acrylamide As salts of sulfonic acid group-containing monomers such as methylpropane sulfonic acid, commercially available products, Eminol JS-20 (manufactured by Sanyo Kasei), Aqualon KH, HS series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Ramtel series (Kao Corporation) Product), Antox series (manufactured by Nippon Emulsifier Co., Ltd.), Adcaria soap (manufactured by ADEKA), spinomer series (manufactured by Solvay), and the like. By using these surfactants and reactive surfactants, or using them in combination, the above polymer emulsion can be obtained. These production methods, the amount of surfactant used, etc. are not particularly limited.

  In addition to the above surfactants and monomers, there is also the introduction of sulfonic acid with persulfate, which is a polymerization initiator used in radical polymerization. In this case, a sulfonic acid ion is introduced into the terminal, and the AC block copolymer used in the present invention forms a salt with the sulfonic acid. As the persulfate initiator, conventionally known ones are used and are not particularly limited. Examples thereof include ammonium persulfate, sodium persulfate, and potassium persulfate, and the amount thereof is not limited. Usually, the amount of these initiators is only a small amount with respect to the monomer. Therefore, it is preferable to ionize the AC block copolymer used in the present invention by using the above-described surfactant or monomer. Good.

  Moreover, the polymer of the polymer emulsion (a) used by this invention is an olefin type, an acryl type, a styrene type, and a vinyl alkanoic acid type | system | group, and those homopolymerization, copolymerization, a grafted product, and a blocked product can be used. Specific examples of the polymer include olefin-based materials such as polyethylene, polypropylene, polyvinyl chloride, polybutadiene, and polyisoprene; acrylic materials include (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, Examples include homopolymers and random copolymers of monomers such as itaconic acid monomers and maleic acid monomers; examples of styrenes include polystyrene and polyvinyl toluene; examples of vinyl alkanoates include vinyl acetate and vinyl butyrate. And the like. Since these monomers having an unsaturated bond can be copolymerized, those copolymers can also be used sufficiently. Further, a bifunctional or higher monomer may be copolymerized to internally crosslink to improve the durability and adhesion of the coating. The composition, molecular weight, production method, and glass transition point of these polymers are not particularly limited, and conventionally known ones are used.

  Next, urethane-based and ester-based polymers that are polymer particles constituting the polymer emulsion (a) used in the present invention will be described. Conventionally known polymers can be used, and the obtained polymers can be obtained by forcibly emulsifying using a surfactant, and structurally a monomer having a sulfonic acid group. It can also be a self-emulsifying polymer emulsion. Moreover, it can be set as the polymer emulsion stabilized by the neutralized carboxyl group and stabilized by use of a sulfonic acid type activator. It is preferable to structurally incorporate a monomer having a sulfonic acid group, because the emulsion is fine and stable.

  The polyurethane is obtained by copolymerizing a monomer having a sulfonic acid group by a conventionally known method. This is not particularly limited. A diol is used as a monomer having a sulfonic acid group, and N, N-bis (2-hydroxyethyl) -taurine, N, N-bis (2-hydroxyethyl) aminomethylsulfonic acid, N, N-bis ( And low molecular diols such as (2-hydroxybutyl) aminoethylsulfonic acid, (1,2-dihydroxypropyl) methylaminoethylsulfonic acid, (1,2-dihydroxypropyl) dodecylaminoethylsulfonic acid. Moreover, although mentioned later, the polyester diol etc. which used 5-sodium sulfo isophthalic acid as a copolymerization component are copolymerized. If necessary, a diol having a carboxylic acid group such as dimethylolbutanoic acid may be used to increase the dispersibility of the polyurethane. By incorporating these sulfonic acids into the structure, a stable polyurethane polymer emulsion can be obtained.

  The isocyanate component, polyol component, and diamine component that is a chain extender for obtaining these urethanes are not particularly limited, and conventionally known ones can be used. Specific examples of the isocyanate component include toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and methylene bisphenyl isocyanate. Examples of the polyol component include glycols such as ethylene glycol and propylene glycol, and polytetramethylene glycol. And the like, polyether diols such as polyhexamethylene carbonate, polyester diols such as polybutane adipate, and the like. Examples of the diamine component include hydrazine, isophorone diisocyanate, and hexamethylene diamine. In addition, polyfunctional alcohols such as triols such as glycerin and polyisocyanates such as burette type can be used. The production method, molecular weight, glass transition point, compounding ratio and the like of these polyurethanes are conventionally known and are not particularly limited.

  Examples of the polyester include polyesters having 5-sodium sulfoisophthalic acid as a copolymerization component. The dicarboxylic acid component and the diol component are not particularly limited, and conventionally known ones are used. Examples of the dicarboxylic acid component include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and adipic acid, their lower alcohol esters, or acid chlorides. Examples of the diol component include ethylene glycol, propylene glycol, polyethylene glycol, and bisphenol A. A diol such as a polyethylene oxide adduct is used, and the aforementioned 5-sodium sulfoisophthalic acid and its lower alkyl ester are used and condensed by dehydration and dealcoholization. In addition, there is no problem if polyfunctional monomers such as trimellitic acid, pyromellitic anhydride, and glycerin are used in combination. The production method, composition, molecular weight, glass transition point and the like are not particularly limited, and conventionally known ones are used.

  As a composite structure of these olefin, acrylic, styrene, vinyl alkanoate, urethane, and ester polymers, graft polymers and block copolymers may be used, and these macromonomers can be used. The polymer can also be obtained by a reaction between polymers, and they are not particularly limited.

  In this invention, although the polymer emulsion (a) comprised with the above polymer particles is used, it is preferable that the particle diameter is 20-300 nm. This is the average particle size as measured by light scattering. In an inkjet, when ejecting from the head, if the particle size is large, the head is clogged, and therefore a nano-sized particle size is preferable. If it is 20 nm or less, it is too fine and the viscosity of the solution increases, and ink jet printing suitability may deteriorate. If it is 300 nm or more, clogging of the head tends to occur. More preferably, it is 50 nm-200 nm.

  The polymer content of the polymer emulsion (a) used is not particularly limited. Moreover, there is no problem even if an organic solvent such as a high-boiling glycol solvent is contained as a film-forming aid as required. The above is the polymer emulsion (a) used in the present invention.

[About polymer emulsion]
The polymer emulsion of the present invention is obtained by the above-mentioned AC block copolymer and polymer emulsion (a), and the salt exchange (ion) of the sulfonate salt of the polymer emulsion (a) and the quaternary ammonium salt of the AC block copolymer. Exchange), the sulfonic acid of the polymer particles of the polymer emulsion (a) (simply referred to as polymer (a)) becomes an anion, and its counter ion is a quaternary ammonium ion of the C polymer of the AC block copolymer. It becomes. In the AC block copolymer, the polymer block of C is a quaternary ammonium salt such as a halide salt. Therefore, when the counter block ion of the sulfonate is used, the AC block copolymer is not a halide salt or the like. For this reason, in the present invention, the AC block copolymer before salt exchange (ion exchange), and the block copolymer in a state in which at least a part of the sulfone ion of the polymer (a) is counterioned after the salt exchange, In order to distinguish these, the counter ion of the sulfonate anion of the polymer (a) is referred to as an AB block copolymer. That is, in the present invention, a polymer block having a carboxy group that needs to be finally neutralized in use of an AC block copolymer is referred to as a polymer block of A as it is, and the polymer block of C is ion-exchanged. A polymer block having a quaternary ammonium cation is called a B polymer block.

  The polymer emulsion of the present invention having the above-described constitution is obtained by simply diluting the polymer emulsion (a), the AC block copolymer, a polymerization solution thereof, a polymerization solution in which their carboxy groups are neutralized, or water with them. It can be easily obtained by adding salt in the form of an aqueous solution. By desalting by mixing, an ion pair of a quaternary ammonium cation is obtained as a sulfonate ion of the polymer (a) and a cation which is a counter ion. For example, if the sulfonate of the polymer (a) is a sodium salt and the quaternary ammonium salt of the AC block copolymer is a quaternary ammonium chloride, sodium chloride is generated and desalted to form a sulfonate anion and a quaternary ammonium chloride. A counter ion of a quaternary ammonium salt is formed. The desalted salt may exist as it is, or may be removed by ion exchange.

  In addition, when solution polymerization of the AC block copolymer is used as it is or when an aqueous solution obtained by diluting the obtained polymerization solution with water is used, in order to neutralize the carboxy group of the polymer A in advance in the polymer emulsion (a). A predetermined amount of alkali may be added, or the polymerization solution is added to the polymer emulsion (a) to generate a counter ion of sulfonic acid and quaternary ammonium salt, and then alkali is added to add carboxy. The group may be neutralized to form an AB block copolymer.

  The polymer emulsion of the present invention comprises a polymer (a) in the polymer emulsion (a) used for this raw material, and an AB block copolymer present in the state of a counter ion of the sulfonate ion of the polymer (a). The ratio is preferably 5 to 50:95 to 50 on a mass basis. If the ratio of the AB block copolymer is less than 5%, the polymer block of A, which is a feature of the present invention, is too few, and the stability of the emulsion cannot be obtained, or the ejection stability is deteriorated when used in ink. This is not preferable because of fear. On the other hand, when the ratio of the AB block copolymer is more than 50%, the polymer (a) is relatively decreased, and the required film physical properties may be insufficient. A more preferable ratio is 10 to 40:60 to 90.

  Further, the ratio of the sulfonate ion to the quaternary ammonium ion of the polymer (a) in the present invention is not particularly limited, and at least a part of the counter ion of the sulfonate ion is a polymer of B of the AB block copolymer. What is necessary is just to become the quaternary ammonium ion which a block has. That is, even if the sulfonate ion is excessive, if the AB block copolymer is in the above range, the effect can be sufficiently exerted. Conversely, even if the quaternary ammonium ion is excessive, the AB block copolymer can be polymer ( Since the sulfonic acid of a) is not ionically bonded and eliminated, the effect of the present invention can be exhibited. Preferably, the sulfonate ion is excessive. This is because there are cases where a large amount of sulfonate ions are contained in order to stabilize the polymer (a), and when all of them are ionized with an AB block copolymer, an A outside the above range of the preferred ratio. This is because the amount of -B block copolymer may be reached.

  The polymer emulsion of the present invention can be easily obtained by desalting (ion exchange) simply by mixing the polymer emulsion (a) and the AC block copolymer as described above. This method is not particularly limited, and can be obtained by stirring and mixing with a disper or the like. You may heat as needed. Moreover, both solid content at the time of mixing is not specifically limited, either, it may mix in a state with high solid content, and may be diluted with water and added as a low concentration. However, if the solid content is too low, the resulting polymer emulsion of the present invention may not be able to achieve a predetermined pigment concentration when used by adding to the colored composition of the present invention. Preferably, the content is 10% by mass or more.

  The polymer particle size of the polymer emulsion of the present invention obtained as described above is the same as the polymer particle size of the polymer emulsion (a) used for the raw material, and the particle size is 20 to 20 300 nm. More preferably, it is 50-200 nm.

  The liquid medium used when preparing the polymer emulsion of the present invention is mainly water, and a water-soluble organic solvent may be used in combination as necessary. As the water-soluble organic solvent, the above-mentioned alcohol, glycol and the like are used, and the amount used is about 0 to 20% by mass in the liquid medium. If it is used in an amount of more than 20% by mass, the organic solvent is taken into the particles, and the particles may swell or aggregate, thereby destroying the dispersion or emulsified state of the polymer emulsion of the present invention. Preferably it is 10 mass% or less.

  The water-soluble organic solvent mentioned above is not particularly limited, and examples thereof include those that can be mixed with 20% by mass or more with respect to water, and a solvent that can be completely mixed is preferable.

  In addition, when preparing the polymer emulsion of this invention, you may add another additive as needed. Specifically, preservatives, pH adjusters, leveling agents, the above-mentioned organic solvents, and further addition of surfactants and the like can be mentioned.

[Use of polymer emulsion]
Next, a colorant composition that uses the emulsion of the present invention as a binder component (film-forming component) and an inkjet ink that uses the same are described. First, the colorant composition of the present invention includes at least a dye and / or pigment, water, a water-soluble organic solvent, and the above-described polymer emulsion of the present invention as constituents. The dyes and pigments used at this time are not particularly limited, and various dyes and pigments conventionally used for printing can be used.

  As for the dye, specifically, an aqueous dye may be used, and an oily dye may be used in some cases. That is, in the case of an oily dye, it does not dissolve in water, but the colorant composition of the present invention may dissolve because of the presence of an organic solvent, or the present invention that constitutes the colorant composition of the present invention. Since an oil-based dye can be contained in the polymer particles of the polymer emulsion, the polymer emulsion may be used even if it is oil-soluble. It does not specifically limit as dye, A conventionally well-known dye is used. For example, various C.I. such as Acid Red, Acid Blue, Acid Yellow, Basic Red, Basic Blue, Basic Violet, Direct Red, Direct Blue, Direct Yellow, Direct Black Oil Red, Oil Blue, Oil Black, and Fluorescent Dye. I. Numbers and dyes from various manufacturers with improved light resistance can be used. Furthermore, a polymer to which a dye is bound can be sufficiently used.

  Examples of the pigment include conventionally known inorganic pigments and organic pigments, and are not particularly limited. Various C.I. I. No. pigments are used, and examples thereof include carbon black pigments, quinacridone pigments, phthalocyanine pigments, benzimidazolone pigments, isoindolinone pigments, azo pigments, and titanium oxide pigments. In particular, 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. And CI Pigment White-6.

  In addition, in the colorant composition of the present invention, a self-dispersing pigment having a water-soluble group introduced on the pigment surface or encapsulated with a resin can also be used as the pigment. For example, examples of self-dispersing pigments include carbon black introduced with acidic groups sold by various carbon black manufacturers, and self-dispersing pigments such as Cabot. One or more of these dyes and pigments are used, and the dye and the pigment may be used in combination.

  The content of these dyes and pigments in the coloring composition is not particularly limited. For example, in the case of a dye, it is preferably used in a range of about 0.5 to 10% by mass, in the case of a pigment, in the case of an organic pigment, about 1 to 30% by mass, and in the case of an inorganic pigment, it is preferably used in a range of about 5 to 60% by mass Is done.

  In the colorant composition of the present invention, water or a water-soluble organic solvent is used as the liquid medium. As the water-soluble organic solvent, the above-mentioned alcohol, glycol, polyhydric alcohol and the like can be used as appropriate, but the blending amount thereof is also not particularly limited. To illustrate again, the water-soluble organic solvents include water-soluble lower aliphatic alcohols such as ethanol and isopropanol, ketone-based water-soluble solvents such as acetone, water-soluble ester solvents such as ethyl lactate, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. Water-soluble ether solvents such as propylene glycol and ethylene glycol, water-soluble glycol solvents such as monoalkyl ethers thereof, water-soluble amide solvents such as N-methylpyrrolidone, water-soluble solvents such as glycerin and 1,2-hexanediol A polyol solvent etc. are mentioned, It does not specifically limit but 1 or more types are used. In consideration of the case where it is used for an inkjet ink, a head such as diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, glycerin, propylene glycol, 1,2-hexanediol, 2-pyrrolidone, or N-methyl-2-pyrrolidone is more preferable. It is preferable to use one or more water-soluble organic solvents for preventing the drying of these.

  The color emulsion composition of the present invention is prepared by adding the polymer emulsion of the present invention to the dyes and / or pigments and liquid medium as described above. The addition amount of the emulsion at that time may be appropriately determined depending on the amount of the polymer component contained in the emulsion in order to obtain the required film performance and coloring power. Preferably, it may be configured to contain 0.5 to 20% by mass of the entire colorant composition, and is adjusted as a film forming component in accordance with the application.

  In the case of a dye, a water-soluble dye can be added to a liquid medium and mixed and dissolved to obtain a colored composition. In the case of an oil-soluble dye, an organic solvent is added and stirred for homogenization so that the dye is dissolved, or is stirred and homogenized so that the dye is incorporated into emulsion particles. In the case of a pigment, in the case of a self-dispersing pigment, it is added to the liquid medium, and the pigment is dispersed by stirring, preferably a dispersion step. In the case of this self-dispersing pigment, a dispersant is not particularly necessary. Examples of the dispersion method include a kneader such as a kneader, two-roll, three-roll, and Miracle KCK (Asada Steel Corporation, trade name), an ultrasonic disperser, and a microfluidizer (high-pressure homogenizer). Mizuho Kogyo Co., Ltd., trade name), Nanomizer (Yoshida Kikai Kogyo Co., Ltd., trade name), Starburst (Sugino Machine Co., Ltd., trade name), G-Smasher (Rix Corporation, trade name) and the like. Moreover, in the thing using bead media, such as glass and a zircon, a ball mill, a sand mill, a horizontal media mill disperser, a colloid mill etc. can be used, There is no limitation in particular and arbitrary methods are taken.

  In the case of a pigment, since the pigment is not dispersed as it is, the pigment is dispersed by the above dispersion method using a pigment dispersant. Conventionally known pigment dispersants are used, for example, random polymers such as acrylic and styrene polymers, block copolymer type dispersants, graft polymer type dispersants, star type polymer dispersants, hyperbranch type dispersions. Agents and the like. The pigment dispersant is used in an arbitrary amount with respect to the pigment. For example, the pigment dispersant is 1 to 100 parts, more preferably 5 to 50 parts, with respect to 100 parts of the pigment.

  In the colored composition of the present invention, the desirable dispersed particle diameter of the pigment is an organic pigment having an average particle diameter of 150 nm or less, considering the color development of the ink such as optical density and saturation and the print quality or the precipitation of the pigment in the ink. The pigment is 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.

  These colorant compositions may contain additives as necessary. As other additives, additives such as a surfactant, a pigment derivative, a leveling agent, an antifoaming agent, and an ultraviolet absorber can be used, and the additive is not particularly limited.

  The colorant composition obtained as described above can be converted into an ink by adding water, a water-soluble organic solvent, and an additive, whereby the aqueous inkjet ink of the present invention can be obtained. For example, in the case of dye ink, the dye concentration is adjusted to 0.5 to 7% by mass, and in the case of pigment ink, the pigment concentration is adjusted to be 1 to 10% by mass. When these inks are used, the addition amount of the emulsion of the present invention is preferably 50 to 300 parts with respect to 100 parts of the dye and / or pigment used in the polymer component contained in the emulsion. When the amount is less than 50 parts, the amount of the dye component is excessively increased and the strength of the coating may not be exhibited. More preferably, it is 50-200 parts.

  Moreover, as described above in the ink of the present invention, additives such as a surfactant, a water-soluble organic solvent, and an antifoaming agent can be used. A surface tension of 20 mN / m or more and 40 mN / m or less is preferably obtained by adding at least a surfactant from the viewpoint of expanding the dot diameter printed by inkjet 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, so it is 0.01 to 5% by mass, preferably 0.1 to 2% by mass.

  The viscosity of the obtained ink is not particularly limited, but is 2 to 10 mPa · s for an inkjet ink containing a dye or an organic pigment, and 5 to 30 mPa · s for an inkjet ink of an inorganic pigment.

  As described above, an ink-jet ink comprising the polymer emulsion of the present invention as a binder component can be obtained. This ink-jet ink can be applied to water-based ink-jet printers for consumer use, industrial use and textile printing. For various media such as plain paper, glossy paper, matte paper, polyester and other films such as PET, fiber such as cotton and polyester, metal such as aluminum plate, etc. Applicable. Further, the polymer emulsion of the present invention is preferably added to the ink jet ink, but can be applied to a substrate in advance or applied as an overcoat on a printed material. Further, it is not limited to inkjet inks, and can be sufficiently used in fields requiring film formation such as water-based paints, inks, and stationery.

  Next, although a synthesis example, 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]
First, the following was charged into a 1-liter separable flask reactor equipped with a stirrer, a back-flow condenser, a thermometer, and a nitrogen inlet tube, and the AC block copolymer defined in the present invention was constructed as follows. A polymer to be a polymer block of A was synthesized. Specifically, to obtain 435.9 parts of diethylene glycol monobutyl ether (hereinafter abbreviated as BDG) as an organic solvent and iodine compound as a polymerization initiating compound, 2.0 parts of iodine, 7.4 parts of 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (hereinafter abbreviated as V-70), 0.22 parts of N-iodosuccinimide as a catalyst, and benzyl methacrylate (Hereinafter abbreviated as BzMA) 123.2 parts and methacrylic acid (hereinafter abbreviated as MAA) 30.1 parts were charged and stirred, and heated to 40 ° C. Since the brown color of iodine disappeared in 3 hours, it was confirmed that V-70 as an initiator reacted with iodine to become a polymerization initiating compound as an iodine compound during this period. Further, polymerization was carried out for 5 hours while maintaining the above temperature, and a part of the reaction solution was sampled at this point. As a result, as described below, it was confirmed that the polymer obtained above had the properties of the polymer block A defined in the present invention.

  First, the solid content of this sample was measured and found to be 27.0%, and the polymerization rate of the monomer used for the raw material calculated based on this was almost 100%. The polymerization rate was also calculated by this method in other examples. Further, when the molecular weight of the solid content of the sampled product was measured by GPC using tetrahydrofuran (hereinafter referred to as THF) as a developing solvent, the number average molecular weight was 4500 and PDI was 1.19. Hereinafter, unless otherwise indicated, the molecular weight is a measured value of GPC using a THF solvent as a developing solvent. Its polymer composition is BzMA / MAA = about 80.4 / 19.6. Further, when this sampled material was added to water, a resin was precipitated, so that it was confirmed that this polymer was a polymer insoluble in water. Furthermore, when a 0.1N KOH ethanol solution using ethanol / toluene as a solvent was measured by titration with phenolphthalein as an indicator, the resin acid value was 129.4 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, a polymer block of C having a quaternary ammonium base is introduced into the polymer having the properties of the polymer block of A defined in the present invention obtained as described above, and an AC type block copolymer is obtained. Was synthesized. First, in the polymer solution obtained above, 14.2 parts of benzyldimethylammonium methacrylate ethyl chloride (hereinafter referred to as DMQ), 61.6 parts of BzMA, and 33. BDG as methacrylate having a quaternary ammonium base. One part, a solution that was previously mixed and homogenized, was added. Then, polymerization was carried out at the same temperature for 4 hours to form a polymer block of C. The obtained polymer solution had a solid content of 40.8%, and the converted polymerization rate was almost 100%. When GPC measurement was performed, the peak was small and unclear. This is probably because the quaternary ammonium base of the introduced polymer block of C has poor solubility in THF and adsorbed on the column. Further, when the molecular weight was measured by GPC using a DMF solvent of 10 mmol / L of lithium bromide as a developing solvent, no peak was observed. It is thought that it was adsorbed similarly.

  When a part of the polymer solution obtained above was added to water, a white emulsion with a slight transparency was obtained. This is because the quaternary ammonium base of DMQ, which is a component of the polymer block of C, has a property of being dissolved in water. This is probably because the polymer portion having the properties of the polymer block A insoluble in water was dispersed as fine particles while the block portion was dissolved in water. From this, it was confirmed that the obtained polymer was a block copolymer in which the polymer block of C was introduced into the polymer having the properties of the polymer block of A. This is referred to as AC block copolymer-1. This block copolymer is in a state where the carboxy group in the structure of the polymer block A is not neutralized with an alkali.

[Synthesis Example 2: Synthesis of AC block copolymer 2]
Using the same apparatus as in Synthesis Example 1, 275.7 parts of BDG, 3.0 parts of iodine, 42.3 parts of methyl methacrylate (hereinafter referred to as MMA), butyl methacrylate (hereinafter referred to as “organic solvent”) as organic solvents. 42.3 parts of BMA), 19.8 parts of 2-ethylhexyl methacrylate (hereinafter referred to as 2-EHMA), poly (n = 2-4) ethylene glycol monomethyl ether methacrylate (Mw = 200, NOF Corporation) Manufactured, hereinafter referred to as PME200), 32.4 parts, MAA 14.4 parts, diphenylmethane (hereinafter referred to as DPM) 0.3 parts as a catalyst, and 11.1 parts V-70 as a polymerization initiator. Then, polymerization was performed at 40 ° C. for 5.5 hours while flowing nitrogen to obtain a polymer block of A. When the solid content of the obtained polymer solution was measured, it was 37.5%, and the converted polymerization conversion was almost 100%. Moreover, Mn was 6000 and PDI was 1.18. It was 61.4 mgKOH / g when the acid value was measured. Moreover, when a part of this polymer solution was added to water, resin precipitated. This indicates that the polymer obtained is insoluble in water. It was confirmed that the polymer obtained from the above has the properties of the polymer block A defined in the present invention.

  Next, in the same manner as in Synthesis Example 1, a C polymer block having a quaternary ammonium base was introduced into the A polymer block obtained above to synthesize an AC block copolymer. First, 71.1 parts of DMQ, 58.2 parts of BzMA, and 166.6 parts of BDG, which were mixed and homogenized in advance, were added to the polymer block solution of A obtained above. And it polymerized at the same temperature for 4 hours, the polymer block of C was formed, and the solution of AC block copolymer was obtained. The obtained polymer solution had a solid content of 41.0%, and the converted polymerization rate was almost 100%. When GPC measurement was performed, the peak was small and unclear as in Synthesis Example 1.

  When a part of the polymer solution obtained above was added to water, it was dispersed in a blue-white translucent state. This is because, like Synthesis Example 1, DMQ-derived quaternary ammonium base, which is a component of the C polymer block, has the property of being dissolved in water. It is considered that the polymer block portion of A that was dissolved in water and insoluble in water was dispersed as fine particles. In addition, since the amount of the introduced quaternary ammonium base is larger than that in Synthesis Example 1 and the polymer block of A contains a large amount of hydrophilic monomer, it is more transparent than that in Synthesis Example 1. Is considered to be a big one. From this, it can be seen that the obtained polymer is an AC block copolymer in which the polymer block of C defined by the present invention is introduced into the polymer block of A defined by the present invention. 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, 366.5 parts of BDG, 3.0 parts of iodine, 21.1 parts of MMA, 21.1 parts of BMA, and 21. 2 of 2-EHMA as organic solvents. 1 part, 83.6 parts of PME200, 14.4 parts of MAA, 0.3 parts of DPM and 11.1 parts of V-70 as a catalyst were polymerized in the same manner as in Synthesis Example 1, A polymer block solution was obtained. The obtained polymer solution had a solid content of 31.0%, and the converted polymerization rate was almost 100%. As a result of GPC measurement, Mn was 6000 and PDI was 1.16. Moreover, the resin acid value of the polymer block of A was 58.2 mgKOH / g.

  Next, in the same manner as in Synthesis Example 1, a C polymer block was introduced into the A polymer block obtained above to synthesize an AC block copolymer. To the polymer block solution of A obtained above, 28.8 parts of DMQ, 84.6 parts of BzMA, 67.2 parts of BDG, and a previously mixed and homogenized solution were added. Polymerization was carried out to form a polymer block of C, and a solution of an AC block copolymer was obtained. The obtained polymer solution had a solid content of 40.1%, 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 dissolved almost transparently. This is presumably because the polymer block of A contains a large amount of polyether. From this, it is considered that the obtained polymer was an AC block copolymer in which the polymer block of C defined by the present invention was introduced into the polymer block of A defined by the present invention. This is referred to as AC block copolymer-3.

  As described above, a block copolymer could be easily obtained by the living radical polymerization method of the present invention using an iodine compound as a polymerization initiating compound and an organic compound as a catalyst. Table 1 shows the number of moles of monomers constituting the polymer block of A with respect to 1 mol of the polymerization initiation compound and the polymer block of C with respect to 1 mol of the polymerization initiation compound for the AC block copolymers obtained in Synthesis Examples 1 to 3 above. The number of moles of the monomer constituting, the content of the monomer having a quaternary ammonium base contained in the AC block copolymer, and the content of the monomer having a quaternary ammonium base contained in the polymer block of C are summarized. Indicated.

[Synthesis Example 4: Synthesis of polymer emulsion (a) -1]
An acrylic styrene-based polymer emulsion stabilized with the sulfonate used in the present invention was prepared in the following manner. Using the apparatus of Synthesis Example 1, 500 parts of water was added and heated to 75 ° C. under a nitrogen stream. In a separate container, 100 parts of styrene, 150 parts of butyl acrylate, and 8.8 parts of Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene allyloxymethyl alkyl ether ammonium sulfate) were mixed to obtain a uniform monomer mixture. . After adding 2.5 parts of potassium persulfate to the synthesizer, the above monomer mixture was added dropwise over 2 hours. Thereafter, the mixture was aged for 3 hours, cooled and taken out. A polymer emulsion (a) -1 which was a white aqueous emulsion was obtained. The solid content was 30.3% and the average particle size was 150 nm. In addition, the used particle size measuring instrument is "NICOMP 380ZLS-S" (made by International Business), and also in the following examples, the measurement of the average particle diameter of the polymer was similarly attempted using this apparatus.

[Synthesis Example 5: Synthesis of polymer emulsion (a) -2]
In the same manner as in Synthesis Example 4, an acrylic polymer emulsion stabilized with a sulfonate used in the present invention was prepared by a conventionally known method as follows. Except for the monomer mixture added in Synthesis Example 4, 150 parts of ethyl acrylate, 96.3 parts of butyl acrylate, 3.7 parts of ethylene glycol dimethacrylate, and 5.9 parts of Aqualon KH-10, In the same manner as in Synthesis Example 4, a polymer emulsion (a) -2 was synthesized. The obtained emulsion was slightly yellowish, had a solid content of 30.5% and an average particle size of 210 nm.

[Comparative Synthesis Example 1: Synthesis of Comparative Polymer Emulsion (a)]
In the same manner as in Synthesis Example 4, an acrylic polymer emulsion having no sulfonate ions was prepared as follows. A white emulsion was prepared in the same manner as in Synthesis Example 4 except that RN-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene nonylpropenyl phenyl ether) was used instead of KH-10 in Synthesis Example 4. A comparative polymer emulsion (a) was obtained. The obtained comparative polymer emulsion (a) had a solid content of 30.2% and an average particle size of 170 nm.

[Synthesis Example 6: Synthesis of polymer emulsion (a) -3]
A urethane-based polymer emulsion stabilized with a sulfonate used in the present invention was prepared as follows by a conventionally known method. Using the same apparatus as in Synthesis Example 1, tetramethylene glycol (hydroxyl value: 37.4 mgKOH / g) 100.0 parts, dimethylolpropionic acid 4.0 parts, isophorone diisocyanate 26.7 parts, acetone 14.5 parts. The mixture was homogenized and reacted for about 6 hours while refluxing acetone to obtain a urethane prepolymer solution. While adjusting the temperature of this urethane prepolymer solution to 40 to 45 ° C., 9.2 parts of isophoronediamine (chain extender), 0.7 part of dibutylamine (polymerization terminator), 63.8 parts of ion-exchanged water, water A mixed solution of 1.2 parts of sodium oxide and 4.2 parts of sodium dodecyl sulfate was added, and a chain extension reaction was performed with vigorous stirring. Furthermore, 212.8 parts of ion-exchanged water was added while emulsifying with stirring. Thereafter, the pressure of the reaction system was reduced and the solvent was removed from the system to obtain a urethane polymer emulsion (a) -3. The obtained polymer emulsion (a) -3 had a solid content of 40.2%, and the amount of carboxy groups in the resin was about 0.21 mmol / g. The average particle size was 53 nm. This is stabilized with a neutralized salt of a carboxy group and a sulfonate derived from sodium dodecyl sulfate as an activator to form an emulsion.

[Synthesis Example 7: Synthesis of polymer emulsion (a) -4]
An ester-based polymer emulsion stabilized with a sulfonate used in the present invention was prepared as follows. A reaction vessel was charged with 95 parts of dimethyl terephthalate, 95 parts of dimethyl isophthalate, 62.4 parts of hexamethylene diol, 55.0 parts of neopentyl glycol, and 0.1 part of tetrabutyl titanate, and gradually heated to 220 ° C. The transesterification was carried out over about 3 hours. Subsequently, 8.4 parts of dimethyl 5-sodium sulfoisophthalate was added, and ester dealcoholization reaction was further performed over 2 hours. Next, 100 parts of Examide M-100 (manufactured by Idemitsu Kosan Co., Ltd., an amide solvent) was added and dissolved, 200 parts of water was added with significant stirring, and 600 parts of water was further added. As a result, a slightly white translucent polymer emulsion (a) -4 was obtained. The obtained ester polymer emulsion (a) -4 had a solid content of 25.3% and an average particle size of 100 nm.

[Confirmation example: Confirmation of counterionization of polymer (a) and AC block copolymer]
In each of the 100 ml flasks, 10 parts of each of the acrylic polymer emulsion (a) -1 obtained in Synthesis Example 4 and the acrylic comparative polymer emulsion (a) obtained in Comparative Synthesis Example were weighed, and 20 parts of water. Diluted respectively.
In a separate container, 1.5 parts of the AC block copolymer-1 obtained in Synthesis Example 1 was weighed and diluted with 13.5 parts of water. Dilution resulted in a white emulsion as described above. This is because the polymer block of A constituting the A-C block copolymer-1 is insoluble in water and thus becomes particles, and the polymer block of C constituting the A-C block copolymer-1 is dissolved in water to form milk. It seems that it became a turbid liquid. That is, in the AC block copolymer-1 in this state, the particle surface is hydrated with the quaternary ammonium salt.
Next, while preparing the diluted solution of the polymer emulsion (a) -1 prepared in the 100 ml flask and the diluted solution of the polymer emulsion obtained in the comparative synthesis example with a stirrer, respectively, A prepared in the above-mentioned separate container -C block copolymer was added to each.
As a result, the polymer emulsion (a) -1 obtained in Synthesis Example 4 was aggregated and precipitated to cause precipitation. In contrast, in the comparative polymer emulsion (a) obtained in Comparative Synthesis Example 1, the emulsion state was maintained as it was, and no precipitation occurred.

  From the above, the “counterionization of the polymer (a) constituting the emulsion and the added AC block copolymer” characterizing the present invention can be confirmed. That is, in the case of the polymer emulsion (a) -1, between the sulfonate salt of the polymer emulsion (a) -1 and the quaternary ammonium salt of the C polymer block of the AC block copolymer-1. When salt exchange (ion exchange) occurs and desalting occurs, the counter ion of the sulfonate ion of the polymer emulsion (a) -1 becomes the quaternary ammonium ion of the AC block copolymer-1, and the polymer block of A Is insoluble in water and is considered to have aggregated and precipitated. On the other hand, in the case of the comparative polymer emulsion (a) obtained in Comparative Synthesis Example 1, since the emulsion is stabilized and emulsified with nonionic polyethylene glycol, the ion exchange as described above is performed even if an AC block copolymer is added. It is considered that each polymer exists as particles and is emulsified. In addition, the above confirms whether or not a commercially available polymer emulsion is stabilized with a sulfonate by using an AC block copolymer in which the polymer block of A is unneutralized. It means you can do it. For this reason, in this invention, the AB block prescribed | regulated by this invention is used by using as a polymer emulsion (a) the commercial item which confirmed that it was stabilized with the sulfonate by the method as mentioned above. The polymer emulsion of the present invention having a copolymer as a counter ion can be easily obtained.

[Example 1: Preparation of polymer emulsion-1 (P-1)]
100 parts of the polymer emulsion (a) -1 obtained in Synthesis Example 4 was weighed into a 300 ml flask, and 0.4 part of 28% aqueous ammonia was added while stirring with a stirrer. In another container, 7.3 parts of the solution of the AC block copolymer-1 obtained in Synthesis Example 1 and 24.3 parts of water were added and mixed to prepare an emulsion. And the emulsion prepared in another container was gradually added, stirring the solution of polymer emulsion (a) -1 previously prepared in the flask. Slight thickening was observed, but the viscosity immediately decreased, no precipitation occurred, and no change in appearance was observed. As described above, a white polymer emulsion-1 of the present invention was obtained. The obtained polymer emulsion-1 had a solid content of 25.0% and an average particle size of 149 nm.

  As described in the confirmation example, the polymer emulsion-1 of the present invention obtained as described above is composed of the sulfonate of the polymer in the polymer emulsion (a) -1 and the first polymer emulsion of the AC block copolymer-1. As the quaternary ammonium salt undergoes salt exchange (ion exchange), the sulfonate of the polymer (a) is ionized by the AB block copolymer, which is a quaternary ammonium ion, and these are counterions. Is. In addition, in the confirmation example, aggregation, precipitation and precipitation occurred, but in this example, the AC block copolymer was added to the polymer emulsion (a) -1 in advance by adding alkaline aqueous ammonia. At that time, the carboxy group contained in the polymer block of A is neutralized and water-solubilized, so that it is considered that the emulsion is stably emulsified without precipitation. The polymer emulsion-1 of the present invention thus obtained was such that the polymer contained in the polymer emulsion (a) -1 and the counter ionized AB block copolymer were in a mass ratio of 100 parts: 10 parts. A polymer emulsion. Hereinafter, this is referred to as P-1.

[Examples 2-3: Preparation of polymer emulsion-2, 3 (P-2, P-3)]
In the same manner as in Example 1, the composition ratio of the polymer (a) contained in the polymer emulsion (a) -1 and the AB block copolymer was 100 parts: 20 parts (Example 2), 100 parts. : 30 parts (Example 3) were prepared. These are referred to as P-2 and P-3, respectively. The solid content of P-2 obtained in Example 2 was 25.1% and the average particle size was 149 nm. The solid content of P-3 obtained in Example 3 was 25.0% and the average particle size was 150 nm. there were. From the results of Examples 1 to 3, it was found that the average particle diameter did not change greatly even when the polymer particles (a) were modified by changing the use ratio of the AB block copolymer to the polymer (a).

[Examples 4 to 10: Preparation of polymer emulsions 4 to 10 (P-4 to P-10)]
In the same manner as in Example 1, each AC block copolymer obtained in Synthesis Examples 1 to 3 and each polymer emulsion (a) obtained in Synthesis Examples 4 to 7 were used at a mass ratio shown in Table 2. Thus, polymer emulsions of Examples 4 to 10 of the present invention were prepared. The properties of the polymer (a) and the AC block copolymer used in the preparation and the resulting polymer emulsion are shown in Table 2 together with the properties of the polymer emulsions of Examples 1 to 3.

[Comparative Example 1: Preparation of polymer emulsion in which AB block copolymer is not a counter ion (Comparative P)]
It carried out similarly using the comparative polymer emulsion (a) obtained in the comparative synthesis example instead of the polymer emulsion (a) -1 used in Example 1. It was the same as the example, and the thickening observed in the example was also confirmed. That is, this thickening is considered to be a phenomenon that occurs when the carboxy group of the polymer block of A is neutralized. The resulting polymer emulsion had a solid content of 25.0% and an average particle size of 150 nm. This is referred to as a comparison P.

[Confirmation Example 2: Stabilization of polymer emulsion]
A 5% aqueous acetic acid solution was prepared in a flask, and polymer emulsions P-1 to P-10 of Examples of the present invention and polymer emulsions (a) -1 to (a) -1 ( When a) -4, comparative polymer emulsion (a) and comparative P of the polymer emulsion obtained in Comparative Example 1 were dropped, P-1 to P-10 of the present invention precipitated and aggregated immediately after dropping. However, the polymer emulsions (a) -1 to (a) -4 used as raw materials to be modified were not changed at all and were diluted as they were. Moreover, in the comparative P of the polymer emulsion, although some agglomerates were observed, it was almost diluted.

This is because in the polymer emulsion of the example of the present invention, the counter ion of the sulfonate ion of the polymer is a quaternary ammonium ion of the polymer block of B and is ionically bonded, and the carboxy group of the polymer block of A is It is stabilized and water-emulsified by neutralization and water solubilization, but the neutralization of the carboxy group is released by the acid of the aqueous acetic acid solution, and the neutralized carboxy group of the polymer block of A is replaced with the carboxy group. This is considered to be because the polymer block of A was insoluble in water and precipitated. In the polymer emulsions (a) -1 to (a) -4 which are raw materials, the sulfonate ions are not neutralized with acetic acid and are stably emulsified as they are, and the nonionic comparative polymer emulsion (a) is Since it does not react with acetic acid at all, it is considered that the emulsification is kept stable as it is. In the comparative P of the polymer emulsion, the comparative polymer emulsion (a) having no sulfonate ion used is stable even in an aqueous acetic acid solution, but the neutralized carboxy group of the AC block copolymer becomes a carboxy group. Thus, it is considered that when water insolubilized, it became slightly unstable and precipitated.
From the above results, the polymer emulsion of the example of the present invention is an emulsion in which the polymer (a) has a polymer stabilized with a sulfonate salt having the AB block copolymer defined in the present invention as a counter ion. It is believed that there is.

[Example 11: Preparation of dye ink]
Polymer emulsions P-1 to P-10 obtained in Examples 1 to 10, polymer emulsions (a) -1 to (a) -4 obtained in Synthesis Examples 4 to 7, and Comparative Synthesis Example 1 The comparative polymer emulsion (a) and the comparative P of the polymer emulsion obtained in Comparative Synthesis Example 2 were respectively used so that the solid content thereof was 2.75 parts, and dye inks were prepared with the following composition. In addition, it adjusted with water so that it might become 100 parts in total, and it was set as the dye ink.
Direct Blue 199 3 parts Each emulsion solid content 2.75 parts 1,2-hexanediol 3 parts Glycerin 15 parts Propylene glycol 15 parts Surfinol 465 (Air Products) 1 part Water remainder The mixture was well mixed and homogenized and filtered through a 10 μm membrane filter to obtain a dye ink.

(Evaluation)
Each dye ink was loaded in a cartridge, and solid printing was performed on each color in a high-speed printing draft mode on Xerox paper 4024 manufactured by Xerox Corporation using an inkjet printer EM930C (trade name) manufactured by Seiko Epson Corporation. As a result, printing with the inks using P-1 to P-10 of Examples 1 to 10 of the present invention does not cause clogging of the print head and prints with blurring and streaking even after printing 100 sheets. It showed a good printing state. However, in the ink when the polymer emulsions (a) -1 to (a) 4 which are raw material emulsions of the polymer emulsion and the comparative polymer emulsion (a) obtained in Comparative Synthesis Example 1 are blended, streaks and Fading was observed, and when observed with an optical microscope, the phenomenon of missing dots was observed. From this, the present invention was modified by reacting the sulfonate group of the polymer particles (a) of the polymer emulsion (a) as a raw material with the A-C block copolymer and treating with the A-B block copolymer. It can be seen that the discharge stability can be improved by the water-solubility of the polymer block of A and the binding property of the polymer block of B to the polymer particles (a). It was confirmed that the use of the binder component makes it possible to provide an ink having excellent ejection stability.

  Further, the printing was stopped and left for 24 hours, and the same printing test was performed again to test the ink re-dissolvability. As a result, the dye inks using the polymer emulsions P-1 to P-10 of Examples 1 to 10 could be printed without problems. However, other comparative inks containing the raw material polymer emulsions (a) -1 to (a) -4, the comparative polymer emulsion (a) and the comparative polymer emulsion P of Comparative Example 1 were all printed. I couldn't. This is because, in the ink of the embodiment of the present invention, the polymer block of A having a high acid value included in the AB block copolymer to be blended in the ink is easily dissolved in water. This is thought to be due to the fact that it is difficult to resist, exhibits re-solubility even after drying, and can be printed even after being left for a long time. Again, the usefulness of the polymer emulsions of the examples of the present invention was confirmed. Moreover, the effect is such that the polymer (a) constituting the polymer emulsion as the raw material and the amount ratio of the AB block copolymer introduced therein, the polymer species of the polymer (a) constituting the polymer emulsion as the raw material, It has been found that even if the type of the introduced AB block copolymer is changed, there is no problem as long as the requirements defined in the present invention are satisfied.

  In addition, any prints obtained with the inks containing the polymer emulsions P-1 to P-10 of the examples and the comparison P of the polymer emulsion of the comparative example 1 are the prints immediately after printing and the prints after being left for 1 hour. Even if it rubs with a finger | toe, it did not detach | leave in any case, but adhesiveness was also favorable. The properties of the polymer (a) were not changed, and it was confirmed that the adhesion effect of the polymer (a) appeared.

[Synthesis Example 7: Block copolymer type pigment dispersant]
Using the living radical polymerization method used in the present invention, a block copolymer type pigment dispersant was prepared as follows. First, the following was charged into a reactor of a 2 liter separable flask equipped with a stirrer, a reverse flow condenser, a thermometer, and a nitrogen introduction tube, and a block copolymer of A was synthesized as follows. Specifically, the above reaction apparatus was charged with 828.4 parts of BDG as an organic solvent, 3.8 parts of iodine, 14.0 parts of V-70, and 0.1 (short for succinimide) as a catalyst. Twenty-two parts, 213.9 parts of BzMA, and 19.8 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) were charged and stirred and heated to 40 ° C. In 3 hours, the brown color of iodine disappeared, and during this period, it was confirmed that V-70 as an initiator reacted with iodine to become a polymerization initiating compound as an iodine compound. Further, polymerization was carried out for 5 hours while maintaining the above temperature, and a part of the reaction solution was sampled at this point. The solid content of this sample was measured and found to be 23.3%, and the polymerization rate calculated based on this was almost 100%. Moreover, when the molecular weight was measured by GPC, Mn was 5500 and PDI was 1.17. The composition of this polymer was BzMA / HEMA = about 90/10. Further, when this sampled material was added to water, a resin was precipitated, and it was confirmed that this polymer was a polymer insoluble in water. A block copolymer of A was obtained as described above.

  Next, the temperature of the reaction solution was set to 40 ° C., 234.8 parts of BzMA and 57.2 parts of MAA were added thereto, and polymerization was performed for 4.5 hours. When a part was sampled at that time, the polymerization rate of the sampled product was almost 100%, and it was confirmed that most of the monomers were polymerized. Moreover, when molecular weight was measured by GPC, it was 10800 in Mn (number average molecular weight) and PDI was 1.23. Since the molecular peak of the polymer block of A shifted to a high molecular weight, and there was almost no peak of the polymer block of A, it was presumed that it became an AC block copolymer as defined in the present invention. Moreover, the molecular weight of the polymer block of C calculated from the number average molecular weight of this AC block copolymer was 10800-5500 = 5300. The polymer block of C has BzMA / MAA = 80.4 / 19.6, and the theoretical acid value of the polymer block of C itself is 127.8 mgKOH / g. The composition of the AC block copolymer is BzMA / HEMA / MAA = 85.3 / 3.8 / 10.9, and the theoretical acid value is 71.1 mgKOH / g. When the acid value of the sample after polymerization was measured by the acid value measuring method described above, the acid value of the AC block copolymer was 71.3 mgKOH / g, which almost coincided with the theoretical value.

  Next, while stirring the polymerization solution obtained above, 40.3 parts of 28% aqueous ammonia and 235.8 parts of water were added, and the solution became transparent and the polymer dissolved. Moreover, when this solution was added to water, it became an almost transparent aqueous solution with a slight bluish tinge. This is presumably because the carboxy group of the C polymer block was neutralized and ionized, and the C polymer block was dissolved in water and thus finely dispersed in the solution. This also suggests that it is an AC block copolymer as defined in the present invention. Moreover, when the solid content of the polymerization solution was measured, it was 33.3%, which almost coincided with the theoretical value in the formulation. This is called a block type dispersant.

[Example 12: Preparation of ink-jet red pigment colorant composition and aqueous pigment ink]
Using the polymer emulsion P-2 prepared in Example 2, a pigment ink was obtained as follows. C. red pigment I. A mill base was prepared by mixing and stirring 200 parts of Pigment Red 122 (dimethylquinacridone pigment: manufactured by Dainichi Seika Kogyo Co., Ltd.), 120 parts of the previously prepared block type dispersant, 80 parts of BDG, and 400 parts of water with a disper. Next, using a horizontal medium disperser “Dynomill 0.6 liter ECM type” (trade name, manufactured by Shinmaru Enterprises Co., Ltd., zirconia beads; 0.5 mm in diameter) is used, and dispersion treatment is performed at a peripheral speed of 10 m / s. went. Dispersion was terminated when dispersed for 2 hours. Next, the dispersion was centrifuged (7500 rpm, 20 minutes), the pigment solution was filtered through a 10 μm membrane filter, and adjusted with ion-exchanged water to obtain a pigment dispersion having a pigment concentration of 14%. . When the average particle diameter of this red aqueous pigment dispersion was measured, the average particle diameter was 100 nm. The viscosity was 3.7 mPa · s.

  Next, an aqueous pigment ink was prepared using the red aqueous pigment dispersion obtained above. 22.4 parts of the polymer emulsion P-2 obtained in Example 2, 1.8 parts of BDG, 5 parts of 1,2-hexanediol, 10 parts of glycerin, and Surfinol 465 are added to 40 parts of the pigment dispersion. 1 part and 20.2 parts of water were added and stirred sufficiently, followed by filtration through a membrane filter having a pore size of 10 μm to obtain a red aqueous pigment ink for inkjet. The viscosity of this ink was 2.8 mPa · s.

[Examples 13 to 15: Preparation of blue, yellow, and black color pigment colorant compositions and aqueous pigment inks for inkjet use]
In the same manner as in Example 12, blue, yellow, and black color pigment colorant compositions for inkjet and each color pigment ink were prepared. That is, instead of the red pigment used in Example 12, C.I. I. Pigment Blue 15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd., cyanine blue A220JC) as a yellow pigment, C.I. I. Pigment Yellow 74 (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika First Yellow 2016G) as a black pigment, C.I. I. Pigment Black 7 (manufactured by Degussa, S170) was used for each to obtain blue, yellow, and black colored pigment dispersions. Table 3 shows the average particle size and viscosity of each pigment dispersion liquid obtained.

  Next, each of the blue, yellow, and black colored pigment dispersions obtained above was used, and the polymer emulsion P-2 used in Example 2 was used to prepare an aqueous pigment ink for ink jet of each color. Specifically, an inkjet blue aqueous pigment ink (viscosity 2.6 mPa · s), an inkjet yellow aqueous pigment ink (viscosity 2.3 mPa · s), and an inkjet black aqueous pigment ink (viscosity 3.23 mPa · s). Obtained. As a result, it was confirmed that low viscosity was achieved in all the prepared inks.

(Evaluation)
Using the red, blue, yellow, and black inks prepared in Examples 12 to 15, high-speed printing tests were performed in the same manner as in Example 11 to evaluate the inks. As a result, it was confirmed that all of the inks exhibited good printability, and even when the ink was dried by the head, it was immediately dissolved and printing was possible. Further, when the respective color inks prepared above were allowed to stand at 70 ° C. for one week, there was no change in the average particle diameter and viscosity.

  Next, using the aqueous pigment ink of each color prepared in Examples 12-15, printing was performed using a vinyl chloride (hereinafter abbreviated as PVC) sheet instead of the plain paper used in the printing test of Example 11. did. And after printing, it put into 70 degreeC drying machine for 5 minutes, and dried. As a result, all the printed parts had good film properties, and the printed material could not be removed even in the cello tape peeling test in which the tape was attached and peeled off at once. That is, all of the above inks showed good film adhesion.

[Examples 16 to 21: Preparation of blue aqueous pigment ink for inkjet using each polymer emulsion]
Using the blue pigment colorant composition obtained in Example 13 and the polymer emulsions (P-4 to P-7, P-9, P-10) of Examples 4 to 7, 9, and 10, respectively, Each blue aqueous pigment ink was prepared in the same manner as described above. The obtained pigment ink was evaluated in the same manner as described above. As a result, it was confirmed that low viscosity was achieved and high storage stability and redispersibility were exhibited.
Subsequently, these inks were used to print on a vinyl chloride sheet, a polyethylene terephthalate (PET) film, and a polypropylene (PP) film, respectively, instead of the plain paper used in the printing test of Example 11. It dried like the said evaluation, and the tape tape peeling test and the scratch test with the nail | claw were done. The evaluation is summarized in Table 4.
(Evaluation criteria)
◎: No change ○: Almost no peeling but slight peeling Δ: Partial peeling is observed ×: The film is peeled off

  As shown in the results of Table 4, depending on the type of polymer constituting the polymer emulsion (a) used as a raw material and the nature of the AB block copolymer introduced therein, depending on the type of substrate printed It was found that the adhesion of the obtained printed matter was changed. Therefore, it is considered effective to appropriately select the type of polymer constituting the polymer emulsion (a) used as a raw material according to each application.

  As a very effective utilization example of the present invention, a part of sulfonate ions contained in a polymer constituting a polymer emulsion stabilized with various kinds of sulfonic acid neutralized salts conventionally used as a binder component of an ink. Alternatively, an inkjet ink to which the polymer emulsion characterizing the present invention is added, in which all counter ions are converted into an AB block copolymer to stabilize the emulsified state. That is, by simply changing the conventional binder component to the polymer emulsion that characterizes the present invention, the ink can be made to have a low viscosity, excellent in high-speed printability and re-dissolvability of the ink, and to the film. Adhesion can also be realized, and an ink-jet ink suitable for an ink-jet printing system compatible with high-speed printing can be provided, and future development is expected.

Claims (16)

A polymer emulsion of a polymer (a) having a sulfonate ion, the emulsion state of which is stabilized by the sulfonate ion and the following AB block copolymer,
Part or all of the counter ion of the sulfonate ion of the polymer (a) is composed of an AB block copolymer composed of 90% by mass or more of a methacrylate monomer,
The polymer block of A constituting the AB block copolymer has a polystyrene-reduced number average molecular weight of 1000 to 20000 in the gel permeation chromatography, and a dispersity (weight average molecular weight / number average molecular weight) indicating the distribution of the molecular weight. ) Is 1.5 or less, and has at least a carboxy group, the acid value of the polymer block is 30 to 250 mgKOH / g, and the carboxy group in the structure is neutralized with an alkali. ,
The polymer block of B constituting the AB block copolymer has at least a quaternary ammonium ion group derived from a methacrylate monomer having a quaternary ammonium salt group used as a forming component thereof.
At least a part of the counter ion of the sulfonate ion of the polymer (a) is a quaternary ammonium ion group of the polymer block of B, and the ion with which the polymer (a) and the AB block copolymer are paired A polymer emulsion characterized by having a bond of   The polymer emulsion according to claim 1, wherein a mass ratio of the polymer (a) to the AB block copolymer is 5 to 50:95 to 50.   The polymer emulsion according to claim 1 or 2, wherein the average particle diameter by light scattering measurement is 20 to 300 nm.   The polymer (a) is selected from the group consisting of olefin-based, acrylic-based, styrene-based, vinyl alkanoate-based, urethane-based and ester-based polymers, or copolymers, graft polymers and block copolymers thereof. The polymer emulsion according to any one of claims 1 to 3, wherein the polymer emulsion is made of at least one kind of material and stabilized with a sulfonate ion.   The polymer emulsion according to any one of claims 1 to 4, wherein the alkali that neutralizes the carboxy group of the polymer block A of the AB block copolymer is ammonia or an organic amine. It is a manufacturing method of the polymer emulsion of Claims 1-4,
(I) a polymer emulsion (a) in which the sulfonate ion of the polymer (a) having a sulfonate ion is neutralized with any of alkali metal, ammonia, or organic amine to form a salt, and the emulsion state is stabilized; An AC block copolymer formed by the following polymer block A and polymer block C is prepared,
The AC block copolymer is a block copolymer composed of 90% by mass or more of a methacrylate monomer, and the polymer block of A has a polystyrene-reduced number average molecular weight of 1000 to 20000 in gel permeation chromatography, and its molecular weight. The dispersity (weight average molecular weight / number average molecular weight) showing the distribution of the polymer is 1.5 or less, has at least a carboxy group, and the acid value of the polymer block is 30 to 250 mgKOH / g, The carboxy group is neutralized with an alkali or subsequently neutralized, and the polymer block of C is at least a group of halide salt, carbonate, hydroxide salt, organic carbonate salt. Comprising at least one quaternary ammonium salt selected from It is formed by monomers containing methacrylate monomer having a grade ammonium ion group,
(II) By adding the AC block copolymer to the polymer emulsion (a), a part or all of the sulfonate ions of the polymer (a) in the polymer emulsion (a) are converted to A- The C polymer block of the AC block copolymer is desalted by ion exchange with the quaternary ammonium ion group constituting the quaternary ammonium salt of the C polymer block of the C block copolymer. A method for producing a polymer emulsion, characterized in that the polymer block is a B polymer block having a quaternary ammonium ion group, and the polymer (a) and an AB block copolymer have a ionic bond forming a pair.   The A-C block copolymer contains a methacrylate monomer unit having the quaternary ammonium salt in a range of at least 5 to 50% by mass in the A-C block copolymer, and the polymer of C The method for producing a polymer emulsion according to claim 6, wherein the polymer emulsion is contained in the block in a range of 15 to 100% by mass.   The method for producing a polymer emulsion according to claim 6 or 7, wherein the alkali for neutralizing the carboxy group of the polymer block A of the AC block copolymer is ammonia or an organic amine.   At least a dye and / or pigment, water, a water-soluble organic solvent, a polymer emulsion according to any one of claims 1 to 5, or a production method according to any one of claims 6 to 8. A colorant composition comprising the polymer emulsion obtained by the above.   An aqueous inkjet ink comprising the colorant composition according to claim 9.   The water-based inkjet ink according to claim 10, wherein the mass ratio of the polymer, which is a constituent component of the polymer emulsion, is 50 to 300 parts with respect to 100 parts of the pigment. A method for producing an AC block copolymer in which 90% by mass or more of the forming component used in the method for producing a polymer emulsion according to claim 6 is a methacrylate monomer,
A mixture of monomers including at least a carboxy group-containing methacrylic acid monomer is subjected to living radical polymerization using at least an iodine compound as a polymerization initiating compound, thereby synthesizing a polymer block of A of the A-C block copolymer. A method for producing an AC block copolymer, comprising polymerizing a mixture of monomers including a methacrylate-based monomer having a quaternary ammonium salt group to synthesize a polymer block C of the AC block copolymer.   13. The A-C block according to claim 12, wherein in the living radical polymerization, the amount of the polymerization initiating compound used is 10 to 150 mol of the total number of moles of monomers forming the C polymer block with respect to 1 mol of the polymerization initiating compound. A method for producing a copolymer.   Further, phosphorus compounds that are phosphorus halides, phosphite compounds, and phosphinate compounds; nitrogen compounds that are imide compounds; oxygen compounds that are phenol compounds; carbonization that are diphenylmethane compounds and cyclopentadiene compounds The method for producing an AC block copolymer according to claim 12 or 13, wherein at least one selected from the group of hydrogen is used as a catalyst.   A polymer emulsion obtained by using at least a dye and / or pigment, water, a water-soluble organic solvent, and an AC block copolymer obtained by the production method according to any one of claims 12 to 14. A colorant composition comprising:   An aqueous inkjet ink comprising the colorant composition according to claim 15.