JP2008088368A - Process for producing composition containing polymer compound, composition and liquid imparting method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a composition which has sufficient dispersion stability and enables control of the adsorption amount and adsorption density of an amphipathic block polymer compound. <P>SOLUTION: The method for producing the composition comprises at least a micelle production step of adsorbing a first amphipathic block polymer compound on a hydrophobic block segment to form a micelle, a crosslinking step of subjecting the first amphipathic block polymer compound to crosslinking reaction within the micelle to produce an adsorption density difference of the first amphipathic block polymer compound, and an additional adsorption step of adsorbing a second amphipathic block polymer compound on the hydrophobic substance after the above crosslinking step, and the first amphipatic block polymer compound is allowed to form a micelle containing the hydrophobic substance in an aqueous solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a composition containing an amphiphilic block polymer compound, a hydrophobic substance, and an aqueous solvent, for example, a method for producing a composition useful as various inkjet inks, a composition obtained thereby, and The present invention relates to a liquid application method.

  In aqueous dispersion materials containing hydrophobic substances, conventionally, as functional materials, herbicides, pesticides such as insecticides, anticancer agents, antiallergic agents, medicines such as anti-inflammatory agents, and inks having colorants, Color materials such as toner are well known. In recent years, digital printing technology has made great progress. Typical examples of the digital printing technology are electrophotographic technology and ink jet technology, but in recent years, the presence of image forming technology in offices, homes, and the like has been increasing.

  Among them, the ink jet technology has a great feature of compactness and low power consumption as a direct recording method. In addition, the image quality is rapidly increasing due to the miniaturization of nozzles. An example of the ink jet technology is a method in which ink supplied from an ink tank is heated by a heater in a nozzle to evaporate and foam, and the ink is ejected to form an image on a recording medium. Another example is a method of ejecting ink from a nozzle by vibrating a piezo element.

  Ink used in these methods usually uses an aqueous dye solution, so that bleeding occurs when colors are superimposed, or a phenomenon called feathering appears in the fiber direction of the paper at the recording location on the recording medium. was there. In order to improve these, the use of pigment-dispersed ink has been studied (Patent Document 1). However, when an organic pigment or carbon black is used as a pigment ink, if the pigment is not very finely dispersed and stabilized, high definition and high color rendering properties cannot be obtained as an ink. If it is not excellent, nozzle clogging may occur easily. Therefore, it is preferable that the ink has excellent dispersion stability and re-dissolvability.

  In addition, the conventional pigment dispersions, when prepared as an ink composition, have been able to realize simultaneously the glossiness of the color image formed thereby, the prevention of bronzing, and the storage stability of the ink composition. Absent. That is, the glossiness of the color image has not been sufficient with the ink compositions obtained by preparing the pigment dispersions so far. Also, due to the particle size distribution of the ejected pigment, the recording surface is colored bronze depending on the viewing angle, so-called bronzing phenomenon cannot be achieved, and high image quality cannot be realized, and the storage stability of the ink composition Was not enough.

Therefore, in recent years, as described in Patent Document 2, a method of physically increasing the dispersion stability by crosslinking the periphery of the pigment with a crosslinkable resin has been used, but further improvement is required. It is a situation.
US Pat. No. 5,085,698 JP 2004-27156 A

  As a result of the study by the present inventors, in order to further improve the image quality, demand for high durability, and improve dispersion stability, the required performance can be improved by increasing the amount of the dispersion resin and various additives. It has been found that there may be. In particular, it has been found that the amount of the dispersed resin adsorbed on the hydrophobic substance affects various performance improvements. However, in the method of merely increasing the amount of the dispersed resin, the required performance is slightly improved, but the viscosity may increase. That is, the amount of empty micelles tends to increase. Although details are unknown, there may be a problem of increased viscosity and decreased ejection stability due to the presence of empty micelles in the ink composition. Since the by-produced empty micelles are generally considered to maintain an equilibrium state with the dispersion, it is difficult to increase the amount of the dispersed resin adsorbed on the hydrophobic substance without increasing the empty micelles. It is done.

  That is, in the dispersion by physical adsorption of the dispersion resin, it is difficult to simultaneously satisfy the state in which the hydrophobic substance is sufficiently coated with sufficient dispersibility and the state in which there are few or no empty micelles.

  In addition, a method of increasing dispersion stability by using a crosslinkable random polymer compound as a dispersion resin and crosslinking around a pigment has been used. The cross-linking of this dispersion resin is aimed at fixing the dispersion resin to the pigment and improving the fastness and glossiness on the media. On the other hand, poor discharge due to increased viscosity or clogging. That was the cause of the phenomenon. This is considered to be caused by the increase in the secondary particle size due to the increase in the amount of the resin bonded to the colorant due to the cross-linking and the aggregation of the colorant.

  In the past, in order to make full use of this contradictory performance, either performance was used in a balance that compromised, or purification was performed by a method such as filtration, so that sufficient effects due to crosslinking were obtained. There was no performance variation.

  An object of this invention is to provide the manufacturing method of the composition which has sufficient dispersion stability and can control the adsorption amount and adsorption density of an amphiphilic block polymer compound.

  As a result of intensive studies on the prior art and problems, the inventors have completed the present invention described below.

  The first invention of the present invention comprises a first amphiphilic block polymer compound comprising a hydrophobic block segment and a hydrophilic block segment and having a crosslinkable functional group, and the first amphiphilic block polymer compound A method for producing a composition comprising a hydrophobic substance encapsulated in micelles formed by an aqueous solvent and an aqueous solvent, wherein the hydrophobic block segment of the first amphiphilic block polymer compound is used as the hydrophobic substance. A micelle manufacturing process for forming micelles by adsorbing, a crosslinking process for crosslinking the first amphiphilic block polymer compound in the micelle, and a hydrophobic block segment and a hydrophilic block segment after the crosslinking process. An additional adsorption step for adsorbing the second amphiphilic block polymer compound to the hydrophobic substance. A method for producing a composition which is symptom. The production method of the present invention has sufficient dispersion stability and can control the adsorption amount and adsorption density of the amphiphilic block polymer compound.

  Preferably, in the method for producing a composition, the second amphiphilic block polymer compound has a crosslinkable functional group. Moreover, it is a manufacturing method of the composition characterized by having the re-crosslinking process which performs the crosslinking reaction which cross-links said 2nd amphiphilic block polymer compound in this micelle after the said additional adsorption process.

  More preferably, the method for producing a composition is characterized in that the additional adsorption step and the recrosslinking step are repeated twice or more.

  2nd invention of this invention is a composition manufactured by the said manufacturing method, It is characterized by the above-mentioned. The composition of the present invention is a composition containing fine polymer composite particles with controlled adsorption amount and adsorption density.

  According to a third aspect of the present invention, there is provided a liquid application method comprising a step of recording an image by applying the composition to a medium. A preferred embodiment of the present invention is a liquid application method for performing recording by ejecting ink from an ink ejection section and applying the ink onto a recording medium. As an ink discharge method, a method in which thermal energy is applied to ink is preferable. In particular, it is preferably used as a pattern forming method for forming a certain pattern on a recording medium or an image forming method for forming an image or characters on a recording medium.

  According to a fourth aspect of the present invention, there is provided a liquid application apparatus used in the liquid application method. Preferably, the image forming apparatus is used as a pattern forming apparatus that forms a certain pattern on a recording medium or an image forming apparatus that forms an image or characters on a recording medium.

  According to the present invention, a composition capable of forming a steric hindrance around a hydrophobic substance and selectively cross-linking at an inner portion of the steric hindrance by using an amphiphilic block polymer compound whose function is separated. And a manufacturing method thereof. Furthermore, the composition which can control the adsorption amount and adsorption density of this amphiphilic block polymer compound, and its manufacturing method can be provided.

  In particular, when a coloring material is used as the hydrophobic substance of the composition, the present invention can provide an ink composition having not only dispersion stability but also low viscosity, excellent dischargeability, and durability.

  As a result of intensive studies on the prior art and problems, the present inventors have completed the present invention.

  A first invention of the present invention contains a first amphiphilic block polymer compound, a hydrophobic substance encapsulated in micelles formed by the first amphiphilic block polymer compound, and an aqueous solvent. It is a manufacturing method of a composition. The first amphiphilic block polymer compound has a hydrophobic block segment and a hydrophilic block segment, and has a crosslinkable functional group. Moreover, it has at least a micelle manufacturing process, a crosslinking process, and an additional adsorption process. In the micelle manufacturing process, micelles are formed by adsorbing the hydrophobic block segment of the first amphiphilic block polymer compound to the hydrophobic substance. In the crosslinking step, the first amphiphilic block polymer compound is subjected to a crosslinking reaction in the micelle. In the additional adsorption step, a second amphiphilic block polymer compound having a hydrophobic block segment and a hydrophilic block segment is adsorbed to the hydrophobic substance after the crosslinking step.

  Examples of the method relating to the micelle production process of the present invention include, but are not limited to, the following methods.

  The micelle production process of the present invention is a constituent component, for example, an amphiphilic block polymer compound having a crosslinkable functional group, a hydrophobic substance, a crosslinking agent, a solvent, an additive and the like are mixed and dissolved or dispersed uniformly. Can be done. A plurality of components are mixed and crushed and dispersed by a dispersing machine such as a sand mill, ball mill, homogenizer, or nanomizer to prepare a mother liquor, and a solvent or an additive is added to adjust the physical properties. By carrying out like this, the hydrophobic block segment of a 1st amphiphilic block polymer compound can be made to adsorb | suck to a hydrophobic substance, and a micelle can be formed. In order to prepare a uniform composition, an emulsion phase inversion method can be preferably used.

  At this time, the crosslinking agent may be added before the dispersion, or may be added as an additive after the dispersion. Moreover, you may use the amphiphilic polymer compound which has a self-crosslinking functional group, without adding a crosslinking agent. Moreover, when using the polymer compound which has a crosslinkable functional group which reacts with the crosslinkable functional group of the said amphiphilic block polymer compound as a crosslinking agent, it is preferable to add before dispersion | distribution.

  Examples of the method relating to the crosslinking step of the present invention include, but are not limited to, the following methods.

  The composition obtained by the preceding micelle manufacturing process is subjected to a crosslinking reaction with a crosslinkable functional group by heating under normal pressure or under pressure, irradiation with energy rays, or a reaction under a specific condition to form a crosslinked bond. Obtainable.

  Examples of the method relating to the additional adsorption step of the present invention include, but are not limited to, the following methods.

  After the previous crosslinking step, the second amphiphilic block polymer compound can be added directly or dissolved in a solvent, and dispersed and additionally adsorbed by a dispersing machine such as a sand mill, ball mill, homogenizer, or nanomizer. Moreover, the emulsification phase inversion method can also be used again like the previous micelle manufacturing process.

  Moreover, you may have the refinement | purification process which removes the unreacted 1st amphiphilic block polymer compound between a bridge | crosslinking process and an additional adsorption process. For example, polymer composite particles in which a hydrophobic substance is coated with a polymer are separated from the composition obtained by the crosslinking step using a centrifuge. Then, the unreacted amphiphilic block polymer compound adsorbed on the polymer composite particles can be removed by washing the polymer composite particles with a solvent in which the amphiphilic block polymer compound is dissolved.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic diagram of a micelle structure obtained by the micelle manufacturing process of the present invention. The state which the dispersion 10 which forms the micelle structure in the aqueous medium is disperse | distributed is shown.

  The dispersion 10 contains a hydrophobic substance 14 and a first amphiphilic block polymer compound 20, and the first amphiphilic block polymer compound 20 includes a hydrophobic block segment 21 and a hydrophilic block segment 22. And have. In the aqueous solvent, the first amphiphilic block polymer compound 20 is included so that the hydrophobic block segment 21 is on the hydrophobic substance 14 side to form a micelle state. 15a shows the crosslinking agent or polymerization initiator which reacts with the crosslinkable functional group which the 1st amphiphilic block polymer compound 20 has.

  Next, a schematic diagram of the micelle structure obtained by the crosslinking step of the present invention is shown in FIG. FIG. 2 shows that the first amphiphilic block polymer compound 20 is crosslinked only in the micelle by the crosslinking step of the present invention, and the adsorption density of the first amphiphilic block polymer compound 20 on the surface layer of the hydrophobic substance 14. The state where the difference has occurred is shown. In this example (FIG. 2), the hydrophobic block segment 21 is provided with a crosslinkable functional group (not shown), and this crosslinkable functional group is bonded to the crosslinkable functional group of another hydrophobic block segment. In some cases, a bond (crosslinked portion 15b) is formed via the crosslinking agent 15a.

  Next, a schematic diagram of the micelle structure obtained by the additional adsorption step of the present invention is shown in FIG. FIG. 3 shows a portion where the surface is partially exposed on the hydrophobic substance 14 (the portion where the adsorption density of the first amphiphilic block polymer compound 20 is low) generated by the crosslinking step by the additional adsorption step of the present invention. 2 shows a state in which the second amphiphilic block polymer compound 20 ′ is adsorbed. Reference numerals 21 'and 22' denote a hydrophobic block segment and a hydrophilic block segment of the second amphiphilic block polymer compound 20 ', respectively.

  In the present invention, it is noted that the adsorption density difference of the first amphiphilic block polymer compound is caused by the cross-linking process, but the adsorption density difference described here is the nonuniformity of the polymer adsorbed on the hydrophobic substance. It refers to the state of simple adsorption or the dense state of the adsorbed polymer.

  This is because when a bond is formed by a cross-linking reaction, the free movement of the polymer is constrained, the density of the polymer is increased, and a bond is easily formed in the vicinity where the bond is formed, which easily causes a difference in the density of the polymer. Become. The difference in adsorption density described in the present invention may be a difference in adsorption density as described above, and the unreacted first amphiphilic block polymer compound is removed by the purification step after the cross-linking step, and is thereby generated. It may be an adsorption density difference. The adsorption density difference described here refers to a site where the second amphiphilic block polymer compound is partially exposed on the hydrophobic substance (first amphiphilic block polymer compound) in the next additional adsorption step. 20 indicates a state in which adsorption can occur to a portion having a low adsorption density.

  The second amphiphilic block polymer compound used in the additional adsorption step of the present invention may have a crosslinkable functional group. When the second amphiphilic block polymer compound has a crosslinkable functional group, it can have a recrosslinking step of causing the second amphiphilic block polymer compound to undergo a crosslinking reaction, for example, in the same manner as in the crosslinking step. . Further, the second amphiphilic block polymer compound used in the additional adsorption step of the present invention may be the same compound as the first amphiphilic block polymer compound or may be different.

  Moreover, as for the introduction position of the crosslinkable functional group in the first amphiphilic block polymer compound, the present invention is preferably contained in the hydrophobic block segment. Moreover, when it contains in a hydrophilic block segment, it is preferable that it is a block segment which does not become the outermost shell of the micelle formed. In this case, intra-micellar cross-linking can occur preferentially in the cross-linking step and / or the re-cross-linking step. That is, cross-linking of polymers in the same micelle is allowed, and cross-linking of other micelles causes the outermost shell hydrophilic block segment to become sterically hindered in an aqueous solvent and inhibit the binding. In the case where the second amphiphilic block polymer compound has a crosslinkable functional group, the crosslinkable functional group is preferably contained in the hydrophobic block segment. Moreover, when it contains in a hydrophilic block segment, it is preferable that it is a block segment which does not become the outermost shell of the micelle formed.

  Therefore, in the configuration of the production method of the present invention, the conventional demerit, which is an advantage of the dispersion resin, which is a merit brought about by cross-linking, while preventing an increase in viscosity and variation in cross-linked state resulting from binding between micelles. Strong fixation to a hydrophobic substance is obtained. Thus, for example, in an ink composition using a pigment as a hydrophobic substance, even if the composition is subjected to a strong impact or the composition is exposed to a high heat atmosphere such as thermal ink jet, the dispersion The state can be good. It is also possible to improve various discharge performances.

  Furthermore, this cross-linking does not release the dispersion resin even on the media, so the chances of the pigment being exposed to the media surface is greatly reduced compared to the conventional case, contributing to improvements in glossiness and fastness. Conceivable.

  Furthermore, in the present invention, the amount of adsorption and the adsorption density of the amphiphilic block polymer compound to the hydrophobic substance can be controlled by repeating the additional adsorption step and the re-crosslinking step twice or more. Therefore, the composition prepared by repeating the previous step can increase the amount of adsorption of the dispersed resin to the hydrophobic substance as compared with the composition prepared only by adding the conventional dispersed resin. Further, an increase in viscosity can be suppressed. As a result, for example, in an ink composition using a pigment as a hydrophobic substance, the dispersion stability can be maintained by increasing the amount of the dispersion resin, and dispersion stability can be maintained even in a high heat atmosphere such as thermal ink jet. Thus, the durability can be improved.

  In the above-described example, the pigment that is a color material is described as the hydrophobic substance included in the dispersion resin, but the present invention is not limited to this. In addition, any hydrophobic substance is included as long as the effect can be obtained by the reliable inclusion of the hydrophobic substance in a harsh environment or when the characteristics of the dispersion can be improved by cross-linking in micelles.

  Next, the amphiphilic block polymer compound used in the present invention will be described.

  The block polymer compound described in the present invention refers to a copolymer in which different types of block segment structures are linked on a polymer chain, and also refers to a block copolymer or a block copolymer.

  “Amphipathic” means that both amphiphilic and lyophobic properties are present, and it is a polymer compound having at least one or more amphiphilic and lyophobic block segments. The above-mentioned amphiphilic property represents a property having a high affinity for a main solvent used in an ink composition described later, and the lyophobic property is a property having a low affinity for a solvent. In the present invention, the main solvent is preferably water, and the amphiphilic block polymer compound used in the present invention preferably has at least one or more hydrophilic and hydrophobic block segments.

  Examples of the hydrophobic block segment in the amphiphilic block polymer compound include a segment containing a repeating unit structure having a hydrophobic group such as an isobutyl group, a t-butyl group, a phenyl group, a biphenyl group, and a naphthyl group. However, it is not limited to these.

  Examples of the hydrophilic block segment in the amphiphilic block polymer compound include a segment containing a repeating unit structure having an ionic group, for example, an organic acid. Preferred examples of organic acids include, but are not limited to, carboxylic acids, sulfonic acids, inorganic salts, and organic salts thereof.

  Furthermore, the amphiphilic block polymer compound used in the present invention may contain a nonionic hydrophilic block segment. By having a nonionic hydrophilic block segment, even if an environmental change such as temperature or pH occurs, the dispersion stability is not impaired, and an ink composition that is particularly excellent in ejectability in the thermal ink jet method can be obtained.

  Each block segment of the amphiphilic block polymer compound used in the present invention may be composed of a repeating unit derived from a single monomer, or may have a structure having a repeating unit derived from a plurality of monomers. Examples of the block segment having a repeating unit derived from a plurality of monomers include a random copolymer and a gradient copolymer whose composition ratio gradually changes.

  The amphiphilic block polymer compound used in the present invention has at least two or more block segments, and can exhibit two or more functions by having two or more block segments. For this reason, it is possible to form a higher-order and precise structure than a polymer compound composed of a single segment. In addition, by maintaining a property similar to a plurality of block segments, it is possible to make the property more stable.

  Examples of the block structure include the following. The present invention includes a diblock polymer AB, an ABA triblock polymer having the same block segment at both ends, a triblock polymer having different block segments, ABC, and those having other polymer units bonded to the triblock structure. For example, a polymer having four different block segments called ABCD, a model called ABCA, and a block polymer having a larger number of block segments are also included in the present invention.

  Further, the first amphiphilic block polymer compound and the second amphiphilic block polymer compound used in the present invention may be the same polymer compound or may be different.

  When the amphiphilic block polymer compound used in the present invention is dispersed together with a hydrophobic substance in a solvent whose main solvent is water, the hydrophilic block segment is located outside, the hydrophobic substance, and the hydrophobic block segment located inside. A core-shell type micelle is formed. Then, a dispersion containing a hydrophobic substance is formed. The dispersion including the hydrophobic substance is preferably a polymer microsphere.

  The micelle of the present invention refers to a micelle structure obtained by dispersing an amphiphilic block polymer compound having both a hydrophilic part and a hydrophobic part in an aqueous solvent, with the hydrophobic part facing inward and the hydrophilic part facing outward. Among them, as described above, it refers to a core-shell type micelle in which the hydrophobic portion is the core and the hydrophilic portion is the shell. The core-shell micelle is generally considered to have a structure in which the hydrophobic core is covered with the hydrophilic shell part, and the influence of the internal hydrophobic core is less likely to appear in the external solvent environment. Details are not clear.

  The polymer microsphere is a general term for micrometer, submicron, and nanometer-order fine particles formed using a polymer as a dispersant. Examples include polymer micelles formed only of polymers, polymer dispersions containing functional substances that are insoluble inside or soluble in polymers in the inner core, and polymer colloids. .

  As a means for confirming the inclusion of the hydrophobic substance, for example, a structure in which the solubility in a solvent changes depending on the temperature is introduced into the block segment of the block polymer compound, and the hydrophobic substance is included in the polymer to change the temperature. The method of investigating the change of the dispersion state is mentioned. Or it can confirm that the hydrophobic substance is included by observing a composition with an electron microscope.

  The empty micelle in the present invention refers to a micelle that does not contain the hydrophobic substance.

  Next, the first and second amphiphilic block polymer compounds used in the present invention will be described in detail.

  The first amphiphilic block polymer compound used in the present invention comprises a hydrophobic block segment and a hydrophilic block segment, and has a crosslinkable functional group. The second amphiphilic block polymer compound used in the present invention comprises a hydrophobic block segment and a hydrophilic block segment. As described above, the second amphiphilic block polymer compound may have a crosslinkable functional group. The first amphiphilic block polymer compound and the second amphiphilic block polymer compound form micelles enclosing a hydrophobic substance, and at least the first amphiphilic block polymer compound is cross-linked with each other. . At the same time, a bond may be formed by a crosslinking reaction of a crosslinkable functional group contained in the second amphiphilic block polymer compound.

  The cross-linking described here refers to a state in which bonds are formed by a cross-linking reaction of cross-linkable functional groups contained in at least the first amphiphilic block polymer compound. When a crosslinkable functional group is contained in the second amphiphilic block polymer compound, a bond may be formed by a crosslinking reaction of the crosslinkable functional group.

  The functional group exhibiting crosslinkability includes a crosslinkable functional group capable of forming a crosslink by reacting with a crosslinker, and a crosslinkable functional group capable of forming a crosslink without a crosslinker (particularly referred to as self-crosslinkable functional group Sometimes).

  Examples of the crosslinkable functional group include a carboxyl group, a hydroxyl group, a tertiary amino group, a blocked isocyanate group, an epoxy group, and a 1,3-dioxolan-2-one-4-yl group. Among these, the reactivity of a carboxyl group, a hydroxyl group, and an epoxy group is high, which is preferable because it can be easily introduced into a resin.

  Next, typical examples of combinations of crosslinkable functional groups and crosslinking agents are listed below.

  When the crosslinkable functional group is a carboxyl group, examples of the crosslinking agent include amino resins, compounds having two or more epoxy groups in one molecule, 1,3-dioxolan-2-one-4-yl groups in one molecule ( And a compound having 2 or more of cyclocarbonate groups).

  When the crosslinkable functional group is a hydroxyl group, examples of the crosslinking agent include amino resins, polyisocyanate compounds, and blocked polyisocyanate compounds.

  When the crosslinkable functional group is a tertiary amino group, the crosslinking agent includes a compound having two or more epoxy groups in one molecule, and a 1,3-dioxolan-2-one-4-yl group in one molecule. Examples thereof include compounds having two or more.

  When the crosslinkable functional group is a blocked isocyanate group, examples of the crosslinking agent include compounds having two or more hydroxyl groups in one molecule.

  When the crosslinkable functional group is an epoxy group or a 1,3-dioxolan-2-one-4-yl group, examples of the crosslinking agent include compounds having two or more carboxyl groups in one molecule, polyamine compounds, polymercapto compounds, etc. Is mentioned.

  Examples of the self-crosslinkable functional group include a radical polymerizable unsaturated group and a hydrolyzable alkoxysilane group. For the purpose of reinforcing self-crosslinkability, a compound having a radically polymerizable unsaturated group, preferably a compound having two or more radically polymerizable unsaturated groups, and a compound having two or more hydrolyzable alkoxysilane groups, respectively Some can be used together.

  Examples of the hydrolyzable alcosilane group include methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (β-methoxyethoxy) silane.

  As the introduction position of the crosslinkable functional group in the amphiphilic block polymer compound, it is preferably contained in the hydrophobic block segment, and when contained in the hydrophilic block segment, the outermost shell of the micelle formed It is preferable that the block segment does not become.

  The crosslinkable functional group contained in the hydrophobic block segment of the amphiphilic block polymer compound used in the present invention preferably does not inhibit the hydrophobicity of the hydrophobic block segment. Specific examples of the functional group include polymerizable unsaturated groups such as isocyanate and epoxy.

  A preferable repeating unit structure of the hydrophobic block segment may be formed only from the repeating unit structure having the crosslinkable functional group. However, a copolymer of the above repeating unit structure having a crosslinkable functional group and a repeating unit structure which is hydrophobic and does not have a crosslinkable functional group is more preferable. More preferably, the structure exhibiting hydrophobicity preferably has a strong interaction with the colorant, and more preferably has an aromatic structure.

  The aromatic described in the present invention refers to a cyclic unsaturated compound such as benzene, and refers to a conjugated unsaturated cyclic compound having a cyclic π electron cloud delocalized above and below the molecular plane. In addition, the aromatic described here may be an aromatic hydrocarbon composed only of a hydrocarbon, or a heteroaromatic compound containing an element other than carbon in the ring structure. Examples thereof include, but are not limited to, benzene, furan, pyridine, biphenyl, phenylpyridine, naphthalene, anthracene, indene and the like.

  In addition, when the hydrophobic block segment is a copolymer of a repeating unit structure having a crosslinkable functional group and a repeating unit structure exhibiting hydrophobicity, it is sufficient to show hydrophobicity as the copolymer. The repeating unit structure having may not be hydrophobic.

  Examples of the copolymer include a random copolymer, a block copolymer, and a gradient copolymer.

  In the preceding copolymer, the content of the repeating unit structure having a crosslinkable functional group contained in the hydrophobic block segment is 1 to 90 mol%, preferably 5 to 80 mol% with respect to the entire hydrophobic block segment. A range is desirable. If the amount is less than 1 mol%, crosslinking may be insufficient. If the amount exceeds 90 mol%, the crosslinking density increases, molecular motion is restricted, and dispersion stability may deteriorate.

  Examples of the hydrophilic block segment include a block segment containing a repeating unit structure having a hydrophilic unit such as a structure containing a large amount of carboxylic acid, carboxylate salt, or hydrophilic oxyethylene unit, and a structure having a hydroxyl group. Specific examples include acrylic acid and methacrylic acid, carboxylates such as inorganic salts and organic salts thereof, polyethylene glycol macromonomers, and hydrophilic monomers such as vinyl alcohol and 2-hydroxyethyl methacrylate. This is a block segment having a repeating unit structure. However, the hydrophilic block segment in the composition of the present invention is not limited to the above structure.

  As a specific example of the amphiphilic block polymer compound used in the present invention, a compound in which the repeating unit structure of the hydrophobic block segment is represented by the following general formulas (1) and (2) is preferable.

  The following general formula (1) represents a repeating unit structure having a crosslinkable functional group, and the following general formula (2) represents a repeating unit structure having no crosslinkable functional group and exhibiting hydrophobicity. A preferable repeating unit structure of the hydrophobic block segment may be formed only of a repeating unit structure having the following general formula (1). However, a copolymer of a repeating unit structure having the following general formula (1) and a repeating unit structure having the following general formula (2) is more preferable.

(In the formula, A represents an optionally substituted alkanetriyl group. G represents a structure selected from a direct single bond, —O—, —OCO—, —OCONH—, —COO—, —CONR ¹ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents 1 to 15 carbon atoms. And a methylene group in the alkanediyl group may be substituted with an oxygen atom or an aromatic ring, and l is from 0 to 30. Represents an integer, and when l is 2 or more, each D may be different from each other, X represents a crosslinkable functional group, and represents a carboxyl group, a hydroxyl group, an amino group, a blocked isocyanate group, an epoxy group, a radically polymerizable group. Saturated group, water content Selected from sexual alkoxysilane group.)
Specific examples of the repeating unit represented by the general formula (1) include

(Ph represents 1,4-phenylene or 1,3-phenylene.)
However, it is not limited to these.

(In the formula, A represents an optionally substituted alkanetriyl group. G represents a structure selected from a direct single bond, —O—, —OCO—, —OCONH—, —COO—, —CONR ¹ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents 1 to 15 carbon atoms. And a methylene group in the alkanediyl group may be substituted with an oxygen atom or an aromatic ring, and l is from 0 to 30. Represents an integer, and when l is 2 or more, each D may be different, E represents an optionally substituted aromatic ring, p represents an integer from 0 to 10, and p is 2 or more In this case, each E may be different.)
Specific examples of the repeating unit represented by the general formula (2) include

(Ph represents 1,4-phenylene or 1,3-phenylene, and Np represents 2,6-naphthyl, 1,4-naphthyl, or 1,5-naphthyl.)
However, it is not limited to these.

  Further, the hydrophobic block segment preferably contains a polyalkenyl ether structure as a repeating unit structure. The content of the polyalkenyl ether structure is preferably 50 mol% or more. In general, a polymer compound having a polyalkenyl ether structure in the main chain has a low glass transition point Tg and flexible molecular mobility. In order to improve dispersion stability and inclusion (encapsulation), the molecular mobility of the block polymer is more flexible because it has a tendency to physically become entangled with the surface of the hydrophobic substance. More preferred.

  Next, a repeating unit structure having an ionic functional group as a hydrophilic block segment is exemplified by the following general formula (3).

(In the formula, A represents an optionally substituted alkanetriyl group. G represents a structure selected from a direct single bond, —O—, —OCO—, —OCONH—, —COO—, —CONR ¹ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents 1 to 15 carbon atoms. And a methylene group in the alkanediyl group may be substituted with an oxygen atom or an aromatic ring, and l is from 0 to 30. Represents an integer, and when l is 2 or more, each D may be different, E represents an optionally substituted aromatic ring, p represents an integer from 0 to 10, and p is 2 or more Each E may be different, R is − ^{OOH, -COOR 2, -COO-M} , -SO 3 H, -SO 3 R 2, .R represents an -SO ₃ -M ² is a linear or branched, substituted having 1 to 5 carbon atoms An alkyl group which may be substituted or an aromatic ring which may be substituted; M represents a monovalent or polyvalent cation.)
Specific examples of the repeating unit represented by the general formula (2) include

(Ph represents 1,4-phenylene or 1,3-phenylene.)
However, it is not limited to these.

  The amphiphilic block polymer compound used in the present invention is characterized by having at least one hydrophobic block segment and one hydrophilic block segment. That is, for example, the amphiphilic block polymer compound having the repeating unit structure represented by the general formulas (1) to (3) described above is satisfied, but other block segments may be included. For example, a repeating unit composed of a nonionic hydrophilic structure in the side chain, more preferably a oxyalkanediyl chain structure, can be mentioned, but is not limited thereto. By having a nonionic hydrophilic block segment, even if an environmental change such as temperature or pH occurs, the dispersion stability is not impaired, and an ink composition that is particularly excellent in ejectability in the thermal ink jet method can be obtained.

  What is preferably used as a specific example of the block segment containing a nonionic hydrophilic structure is a compound containing a repeating unit represented by the following general formula (4).

(In the formula, A represents an optionally substituted alkanetriyl group. G represents a structure selected from a direct single bond, —O—, —OCO—, —OCONH—, —COO—, —CONR ¹ —. R ¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and D represents 1 to 15 carbon atoms. And a methylene group in the alkanediyl group may be substituted with an oxygen atom or an aromatic ring, and O represents an oxygen atom. l represents an integer from 0 to 30, and when D is 2 or more, each D may be different from each other, J is a hydrogen atom, a linear or branched substituted group having 1 to 5 carbon atoms Represents an optionally substituted alkyl group.)
Specific examples of the repeating unit represented by the general formula (4) include

However, it is not limited to these.

  More preferably, the hydrophilic block segment preferably contains a polyalkenyl ether structure as a repeating unit structure in the same manner as the hydrophobic block segment. The content of the polyalkenyl ether structure is preferably 50 mol% or more. As previously described, a polymer compound having a polyalkenyl ether structure in the main chain generally has a low glass transition point (Tg) and a flexible molecular mobility. The molecular mobility of the hydrophilic block segment that forms the outermost shell of the micelle is more flexible, so that it is easy to solvate in the solvent and to be entangled with each other on the recording medium. Therefore, it is more preferable. That is, it is more preferable to contain a polyalkenyl ether structure as a repeating unit structure from the viewpoint of improving dispersion stability and improving the ability to form a coating layer on a recording medium.

  The content ratio (mass basis) of the hydrophobic block segment and the hydrophilic block segment contained in the amphiphilic block polymer compound used in the present invention is preferably 5:95 to 95: 5, and 10:90 to 90: A range of 10 is more preferred.

  Further, the number average molecular weight (Mn) of the amphiphilic block polymer compound used in the present invention is preferably 200 or more and 10000000 or less, and more preferably 1000 or more and 1000000 or less. If it exceeds 10000000, the entanglement between the polymer chains and between the polymer chains becomes excessive, and it is difficult to disperse in the solvent. If it is less than 200, the steric effect as a polymer may be difficult to obtain due to the low molecular weight. The preferable degree of polymerization of each block segment is 3 or more and 10,000 or less. More preferably, it is 5 or more and 5000 or less. More preferably, it is 10 or more and 4000 or less.

Polymerization of the block polymer compound used in the present invention is often carried out by cationic polymerization, anionic polymerization, radical polymerization or the like. In the case of cationic polymerization, the initiator includes a protonic acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, perchloric acid, BF ₃ , AlCl ₃ , TiCl ₄ , SnCl ₄ , FeCl _3. , RAlCl ₂ , R _1.5 AlCl _1.5 (R represents alkyl), etc., and a combination of a Lewis acid and a cation source (the cation source includes a protonic acid, water, alcohol, an adduct of vinyl ether and sulfonic acid, etc.). Take as an example. By causing these initiators to coexist with a polymerizable compound (monomer), the polymerization reaction proceeds and a block polymer compound can be synthesized.

The polymerization method that is more preferably used in the present invention will be described. A number of methods for synthesizing polymers containing a polyvinyl ether structure have been reported (for example, JP-A-11-080221). A method by cation living polymerization by Aoshima et al. (Polymer Bulletin Vol. 15, 417, 1986, Japanese Patent Laid-Open Nos. 11-322942 and 11-322866) is representative. Accurate length (molecular weight) of various polymers such as homopolymers, copolymers composed of two or more monomers, block polymers, graft polymers, gradient polymers, etc. Can be synthesized to match. In addition, living polymerization can also be carried out in the HI / I ₂ system, HCl / SnCl ₄ system, or the like.

  The content of the amphiphilic block polymer compound contained in the composition obtained by the production method of the present invention is preferably in the range of 0.1% by mass to 90% by mass. More preferably, it is 1 mass% or more and 80 mass% or less. In addition, this content means the sum total of a 1st amphiphilic block polymer compound and a 2nd amphiphilic block polymer compound. The content ratio (mass basis) of the first amphiphilic block polymer compound and the second amphiphilic block polymer compound is preferably 5:95 to 99: 1.

  Next, the hydrophobic substance used in the present invention will be described in detail.

  The hydrophobic substance contained in the composition of the present invention is a substance that is insoluble in water. Insoluble in water is a property that does not dissolve or stably disperse in water. Specifically, it indicates that the solubility of the compound in water is 1 g / L or less, or that a stable dispersion in water is not formed.

  Examples of the hydrophobic substance used in the present invention include hydrophobic functional substances such as pigments, metal particles, organic fine particles, inorganic fine particles, magnetic particles, organic semiconductors, conductive materials, optical materials, and nonlinear optical materials. However, it is not limited to these.

  The hydrophobic material included in the present invention is preferably a coloring material such as a pigment and a dye, and more preferably a pigment.

  Specific examples of pigments and dyes when the composition obtained by the present invention is used as an ink composition are shown below.

  The pigment may be either an organic pigment or an inorganic pigment, and the pigment used in the ink is preferably a black pigment and three primary color pigments of cyan, magenta, and yellow. Color pigments other than those described above, colorless or light color pigments, metallic luster pigments, and the like may be used. In the present invention, commercially available pigments may be used, or newly synthesized pigments may be used.

  The following are examples of commercially available pigments for black, cyan, magenta, and yellow.

  Examples of black pigments include Raven 1060 (trade name, manufactured by Colombian Carbon), MOGUL-L (trade name, manufactured by Cabot), Color Black FW1 (trade name, manufactured by Degussa), MA100 (trade name, Mitsubishi Chemical). However, it is not limited to these.

  Examples of cyan pigments include C.I. I. Pigment Blue-15: 3, C.I. I. Pigment Blue-15: 4, C.I. I. Pigment Blue-16, and the like, but are not limited thereto.

  Examples of magenta pigments include C.I. I. Pigment Red-122, C.I. I. Pigment Red-123, C.I. I. Pigment Red-146 and the like, but are not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow-74, C.I. I. Pigment Yellow-128, C.I. I. Pigment Yellow-129 and the like, but are not limited thereto.

  In the composition of the present invention, a pigment that is self-dispersible in water can also be used. Water-dispersible pigments include those using the steric hindrance effect in which a polymer is adsorbed on the pigment surface and those using electrostatic repulsion. Examples of commercially available products include CAB-0-JET200, CAB-0-JET300 (trade names, trade names manufactured by Cabot Corporation), Microjet Black CW-1 (trade names, manufactured by Orient Chemical Co., Ltd.), and the like.

  The hydrophobic substance used in the present invention is preferably 0.1 to 50% by mass with respect to the total mass of the composition. When the amount of the hydrophobic substance is 0.1% by mass or more, a preferable image density is obtained, and when it is 50% by mass or less, preferable dispersion is obtained. A more preferable range is 0.5 to 30% by mass.

  In the present invention, a dye may be used in combination.

  In addition, the present invention can also contain additives such as ultraviolet absorbers, antioxidants, stabilizers and the like without inhibiting the inclusion of components other than those described above.

[Other ingredients]
The components other than the amphiphilic block polymer compound and the hydrophobic substance contained in the present invention will be described in detail. Other components include aqueous solvents, additives, crosslinkers and the like.

[Aqueous solvent]
The composition of the present invention contains an aqueous solvent. The aqueous solvent in the present invention is mainly composed of water, and may contain an organic solvent or an aqueous solvent in addition to water as long as the block polymer compound maintains a dispersed state in a micelle state. . As water, ion-exchanged water, pure water and ultrapure water from which metal ions and the like have been removed are preferable. Examples of the organic solvent include non-aqueous solvents such as hydrocarbon solvents, aromatic solvents, ether solvents, ketone solvents, ester solvents, amide solvents. Examples of the aqueous solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, and glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol Polyhydric alcohol ethers such as monoethyl ether and diethylene glycol monobutyl ether; nitrogen-containing solvents such as N-methyl-2-pyrrolidone, substituted pyrrolidone and triethanolamine; In addition, monohydric alcohols such as methanol, ethanol and isopropyl alcohol can be used for the purpose of accelerating the drying of the aqueous dispersion on the recording medium.

  In this invention, it is preferable to use content of the said aqueous solvent in the range of 9.9-95 mass% with respect to the total mass of a composition. More preferably, it is the range of 19.5-90 mass%.

[Additive]
In the present invention, various additives, auxiliaries and the like can be added as necessary. One additive is a dispersion stabilizer that stably disperses a pigment in a solvent. The present invention has a function of dispersing a hydrophobic substance such as a pigment by an amphiphilic block polymer compound, but if the dispersion is insufficient, another dispersion stabilizer may be added. Good.

  As another dispersion stabilizer, it is possible to use a resin or a surfactant having both hydrophilic and hydrophobic portions. Examples of the resin having both hydrophilic and hydrophobic parts include a copolymer of a hydrophilic monomer and a hydrophobic monomer.

  Examples of the hydrophilic monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, or the above carboxylic acid monoesters, vinyl sulfonic acid, styrene sulfonic acid, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, and the like. Examples of the hydrophobic monomer include styrene derivatives such as styrene and α-methylstyrene, vinylcyclohexane, vinylnaphthalene derivatives, acrylic acid esters, and methacrylic acid esters. Copolymers having various configurations such as random, block, and graft copolymers can be used. Of course, both hydrophilic and hydrophobic monomers are not limited to those shown above.

  As the surfactant, an anionic, nonionic, cationic or amphoteric surfactant can be used. Anionic activators include fatty acid salts, alkyl sulfate esters, alkylaryl sulfonates, alkyl diaryl ether disulfonates, dialkyl sulfosuccinates, alkyl phosphates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyls. Examples thereof include phosphate ester salts and glycerol borate fatty acid esters. Nonionic activators include polyoxyethylene alkyl ethers, polyoxyethyleneoxypropylene block copolymers, sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based, silicon-based and the like. It is done. Examples of the cationic activator include alkylamine salts, quaternary ammonium salts, alkylpyridinium salts, alkylimidazolium salts and the like. Examples of amphoteric activators include alkylbetaines, alkylamine oxides, phosphadylcholines, and the like. Similarly, the surfactant is not limited to the above.

  Other additives include, for example, a pH adjuster, a penetrating agent, an antifungal agent, a chelating agent, an antifoaming agent, an antioxidant, an antifungal agent, a viscosity adjusting agent, a conductive agent, and an ultraviolet ray. Absorbers and the like can also be added. The pH adjusting agent is used to obtain stability of ink and stability of ink piping in the recording apparatus. The penetrant accelerates the penetration of the ink into the recording medium and accelerates the apparent drying. The antifungal agent prevents the generation of wrinkles in the ink. The chelating agent sequesters metal ions in the ink and prevents the deposition of metal at the nozzle portion and the insoluble matter in the ink. The antifoaming agent prevents the occurrence of bubbles during the circulation or movement of the recording liquid or during the production of the recording liquid.

  Furthermore, in the present invention, polymer fine particles may be added. The polymer fine particles of the present invention are compounds added for the purpose of exhibiting functions such as fastness, color development, gloss, bronze suppression, bleed suppression, and specifically include emulsion fine particles, polymer interfaces. Examples include activators.

  Examples of the resin component constituting the emulsion fine particles and the polymer surfactant include acrylic resins, methacrylic resins, styrene resins, urethane resins, acrylamide resins, epoxy resins, and the like. A mixed system of Among these resin components, a styrene-acrylic acid copolymer, a styrene-acrylic acid-acrylic acid alkyl ester copolymer, a styrene-maleic acid copolymer, and a styrene-maleic acid-acrylic acid alkyl ester copolymer are more preferable. Examples thereof include a polymer, a styrene-methacrylic acid copolymer, a styrene-methacrylic acid-acrylic acid alkyl ester copolymer, and a styrene-maleic acid-half ester copolymer.

  Such resin emulsions may be synthesized and used so as to satisfy various characteristics, but commercially available products may also be used. Similarly, the polymer fine particles are not limited to the above.

[Crosslinking agent]
In this invention, the crosslinking agent selected by the combination of the above-mentioned crosslinkable functional group and crosslinking agent can be added. The cross-linking agent is added before or after the hydrophobic substance is dispersed. Since the probability of the presence of a crosslinking agent on the surface of the hydrophobic substance is high at that time, it is more preferable before the dispersion.

  Cross-linking of the amphiphilic block polymer compound used in the present invention is performed as follows. First, the amphiphilic block polymer compound, hydrophobic substance, and crosslinking agent are dispersed in an aqueous medium composed of water and, if necessary, a water-soluble organic solvent. And after forming a polymer microsphere as a dispersion, it carries out by the heating under normal pressure or pressurization, irradiation of energy rays, etc. In this case, crosslinking may be performed in the presence of a catalyst or a polymerization initiator.

  Regarding the solid content concentration in the dispersion when crosslinking is performed, when the solid content concentration in the dispersion liquid is high, the distance between dispersed pigments may be short and the pigments may be aggregated by crosslinking. Therefore, it is preferable to adjust the concentration by adding water or the like in advance, and set it in a range of 20% by mass or less, and more preferably in a range of 0.1 to 15% by mass.

  Self-crosslinking by a carboxyl group and an epoxy group, self-crosslinking by a hydroxyl group and an N-alkoxymethylamide group, and self-crosslinking by a hydrolyzable alkoxysilane group are, for example, crosslinking by heating at 50 to 150 ° C. under normal pressure or pressure. Can be mentioned. In this case, it is also recommended to use a catalyst.

  In the case of self-crosslinking with a radically polymerizable unsaturated group, a water-soluble polymerization initiator such as potassium persulfate or ammonia persulfate is added, and the polymerization is made redox, and the temperature is about 50 to 90 ° C. Can be crosslinked.

  On the other hand, the crosslinking using a crosslinking agent is preferably performed by heating at 50 to 100 ° C. under normal pressure, but in some cases, the crosslinking can be performed at about 100 to 150 ° C. under pressure. In this case, it is also recommended to use a catalyst.

  The crosslinking agent that can be added to the present invention is preferably a hydrophobic compound. Since the crosslinkable functional group is contained in the hydrophobic block segment in the amphiphilic block polymer compound, the crosslinking agent used in the present invention is preferably a hydrophobic one, but a water-soluble or water-dispersible one is used. You can also

  The crosslinking agent included in the present invention may be a polymer compound.

  The blending ratio of the amphiphilic block polymer compound and the crosslinking agent is generally preferably in the range of 30:70 to 95: 5, particularly preferably in the range of 40:60 to 90:10, in terms of the solid mass ratio.

  The second invention of the present invention will be described.

  2nd invention of this invention is the composition manufactured by the manufacturing method which is 1st invention of this invention.

  The composition of the present invention is an aqueous composition containing a solvent. An aqueous composition is a composition whose main solvent is water. The composition of the present invention is preferably an ink composition. More preferred is an inkjet composition. The ink jet composition is a composition that can be ejected by an ink ejection method using an ink jet method to be described later.

  In general, ink jet compositions may have stricter conditions for composition characteristics such as viscosity, size of dispersed fine particles, and storage stability, as compared with ink compositions. In the ejection method based on the ink jet method, the composition is ejected through a fine nozzle. Therefore, the viscosity of the composition is particularly low, the size of fine particles in the composition is small, and the storage stability is preferably excellent.

  Next, a liquid application method and a liquid application apparatus, which are the third and fourth aspects of the present invention, will be described using the composition according to the second aspect of the present invention.

[Liquid application method, liquid application apparatus]
The composition of the present invention can be used in various image forming methods and apparatuses such as various printing methods, ink jet methods, and electrophotographic methods, and can be drawn by an image forming method using this device. Moreover, when using a liquid composition, it can be used for the liquid provision method for forming a fine pattern in the inkjet method etc. or administering a medicine.

  The image forming method of the present invention is a method for forming an excellent image with the composition of the present invention. The image forming method of the present invention is preferably an image forming method in which recording is performed by ejecting the ink composition of the present invention from an ink ejecting portion and applying it onto a recording medium. For image formation, a method using an ink jet method in which thermal energy is applied to the ink to discharge the ink is preferably used.

  As an inkjet printer using the inkjet ink composition of the present invention, various inkjet recording apparatuses such as a piezo inkjet system using a piezoelectric element and a bubble jet (registered trademark) system that records by foaming by applying thermal energy are used. Applicable to.

  Among them, the present invention uses a means (for example, an electrothermal converter or a laser beam) that generates thermal energy as energy used for ejecting ink jet ink that has strict ink dispersion conditions. In particular, it has a particularly excellent effect.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

<Synthesis of hydrophobic polymer cross-linking agent>
(Synthesis Example 1)
Synthesis of Random Polymer Compound of 4-Methylbenzeneoxyethyl Vinyl Ether (TolOVE) and 2-Vinyloxyethyl Methacrylate (VEMA) After replacing the inside of a glass container equipped with a three-way stopcock with nitrogen, it was heated to 250 ° C. in a nitrogen gas atmosphere. Adsorbed water was removed. After returning the system to room temperature, the following components were added to cool the reaction system.
・ 4-Methylbenzeneoxyethyl vinyl ether (TolOVE)
15 mmol
・ 2-vinyloxyethyl methacrylate (VEMA) 15 mmol
・ Ethyl acetate 160mmol
1-isobutoxyethyl acetate 0.5 mmol
・ Toluene 110ml
When the system temperature reached 0 ° C., 2.0 mmol of ethylaluminum sesquichloride (an equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride) was added to initiate polymerization. Monitoring was performed using gel permeation chromatography (GPC) whose molecular weight was divided in time, and the polymerization reaction was stopped when Mn was 7000. The polymerization reaction was stopped by adding a 0.3% by mass ammonia / methanol aqueous solution to the system. The reaction mixture solution was diluted with dichloromethane and washed 3 times with 0.6M hydrochloric acid and then 3 times with distilled water. The organic phase obtained was concentrated and dried with an evaporator, and then vacuum-dried, then repeatedly dialyzed in a methanol solvent using a cellulose semipermeable membrane to remove the monomeric compound, and the target hydrophobic A functional polymer crosslinking agent was obtained. The compound was identified using NMR and GPC. Mn = 7000, Mw / Mn = 1.20, and the polymerization degree ratio was TolOVE: VEMA = 1: 1.

<Synthesis of amphiphilic block polymer compound>
(Synthesis Example 2)
Synthesis of triblock polymer compound A block: 4-methylbenzeneoxyethyl vinyl ether (TolOVE) and 2-vinyloxyethyl methacrylate (VEMA)
B block: Methoxyethoxyethyl vinyl ether (MOEOVE)
C block: 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEtPhCOOTBDMSi)
Polymerization was carried out in the same manner as in Synthesis Example 1 except that 4-methylbenzeneoxyethyl vinyl ether (TolOVE) was changed to 20 mmol (mmol) and 2-vinyloxyethyl methacrylate (VEMA) was changed to 20 mmol. GPC monitoring confirmed the completion of polymerization of the A block (Mn at this stage = 12300, Mw / Mn = 1.18). Next, 30 mmol of methoxyethoxyethyl vinyl ether (MOEOVE), which is a monomer of the B block, was added to continue the polymerization. Monitoring using GPC confirmed the completion of polymerization of the B block (Mn at this stage = 15100, Mw / Mn = 1.26). Then, 15 mmol of 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi), which is a monomer of the C block, was added to continue the polymerization. The polymerization reaction was stopped when 50 mol% of the monomer of the C block was polymerized by monitoring using GPC. The polymerization reaction was stopped by adding a 0.3% by mass ammonia / methanol aqueous solution to the system. The reaction mixture solution was diluted with dichloromethane and washed 3 times with 0.6M hydrochloric acid and then 3 times with distilled water. The obtained organic phase was concentrated and dried with an evaporator, and the target block polymer was isolated from what was vacuum-dried. The block polymer was identified using NMR and GPC. Mn = 18000, Mw / Mn = 1.27, and the polymerization degree ratio was A: B: C = 80: 60: 15. Moreover, the polymerization degree ratio in A segment was TolOVE: VEMA = 1: 1.

  Next, 1 g of the obtained block polymer was dissolved in 45 ml of THF, 5 ml of 3N HCl / ethanol solution was added, and the mixture was stirred at room temperature (23 ° C.) for 3 hours, and then 20 ml of ethanol was added and further stirred for 3 hours. The reaction was monitored by NMR. After 100% hydrolysis was completed, the reaction was neutralized with sodium carbonate to complete the reaction. The reaction solution was filtered, concentrated with an evaporator, extracted with methylene chloride and dried, and then the solvent was distilled off to obtain a block polymer compound in which the side chain of the C block was a free carboxylic acid polymer. Further, it was confirmed by NMR that almost all VEMA double bonds remained.

  Furthermore, neutralization was performed with an equal amount of 1N sodium hydroxide, and water was distilled off to obtain an amphiphilic block polymer compound 1 in which the side chain of the C block was a sodium carboxylate.

  In the above experimental operation, in order to suppress the reaction of the unsaturated bond of VEMA, concentration by an evaporator and distillation of water were performed at a low temperature of 40 ° C. or less.

<Amphiphilic block polymer compound having a polymerizable unsaturated group at one end>
(Synthesis Example 3)
Synthesis of Polymerization Initiating Species VEMA that had been purified in advance by distillation under reduced pressure at 45 to 50 ° C./0 mmHg and 10 molar equivalents of acetic acid were mixed and stirred at room temperature for 1 day. The obtained reaction completion liquid was dissolved in hexane and washed with an alkaline aqueous solution to remove unreacted acetic acid. Subsequently, after hexane was distilled off by the obtained solution evaporator, drying under reduced pressure was performed for 1 day or more to obtain a target cation living polymerization initiator (VEM-OAc). The synthesized compound was identified by NMR.

(Synthesis Example 4)
Synthesis of triblock polymer having a polymerizable unsaturated group at one end A block: 4-methylbenzeneoxyethyl vinyl ether (TolOVE)
B block: Methoxyethoxyethyl vinyl ether (MOEOVE)
C block: 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEtPhCOOTBDMSi)
In the same manner as in Synthesis Example 2, the monomer of the A block is changed to 40 mmol (mmol) of 4-methylbenzeneoxyethyl vinyl ether (TolOVE), and 1-isobutoxyethyl acetate is changed to VEM-OAc synthesized in Synthesis Example 3. Polymerization was performed. The block polymer was identified using NMR and GPC. Mn = 17200, Mw / Mn = 1.24, and the polymerization degree ratio was A: B: C = 80: 60: 15.

  By the same post-treatment as in Synthesis Example 2, an amphiphilic block polymer compound 2 in which the side chain of the C block was a sodium carboxylate was obtained.

(Example 1) Micelle manufacturing process-crosslinking process-additional adsorption process <Micelle manufacturing process 1>
The following components were dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes.
-Hydrophobic polymer crosslinking agent of Synthesis Example 1 1 part by mass-Amphiphilic block polymer compound 2 having a polymerizable unsaturated group at one end of Synthesis Example 4
2 parts by mass / coloring material (carbon black, trade name: S160, manufactured by Degussa) 6 parts by mass Thereafter, 90 parts by mass of distilled water is added to convert to an aqueous phase, and the pH is adjusted to 9 using an aqueous sodium hydroxide solution. It was adjusted. Further, 0.05 parts by mass of azobisisobutyronitrile (AIBN) was added thereto, and tetrahydrofuran was removed by distillation under reduced pressure to obtain a dispersion composition.

The carbon black S160 (trade name) used here is a high structure pigment having a particle size (D) of 20 nm, an oil absorption amount (DBP absorption) of 150 ml / 100 g, and an N ₂ adsorption amount (SN ₂ ) of 150 m ² / g. is there.

<Crosslinking step 1>
Subsequently, the dispersion composition obtained in the micelle production step 1 was heated at a temperature of 60 ° C. for 48 hours to carry out a crosslinking reaction, thereby obtaining an intermicellar crosslinked dispersion composition. The progress of the crosslinking reaction was performed by identification of the double bond portion using ¹³ C-NMR.

<Additional adsorption process 1>
The amphiphilic block polymer compound 2 of Synthesis Example 4 was dissolved in 2 parts by mass of THF and added to the dispersion composition obtained in the crosslinking step 1. After dispersing with an ultrasonic homogenizer for 10 minutes, the pH was adjusted to 9 using an aqueous sodium hydroxide solution. Dispersion composition 1 was obtained by removing tetrahydrofuran by distillation under reduced pressure.

Subsequently, an ink composition 1 was prepared using the obtained dispersion composition 1 so as to have the following composition.
-Aqueous pigment dispersion 25 parts by weight-Glycerol 8 parts by weight-Ethylene glycol 5 parts by weight-Ethanol 5 parts by weight-Emulgen 120 (trade name, manufactured by Kao Corporation) 0.05 parts by weight-Water 57 parts by weight (Examples) 2) Micelle manufacturing process-crosslinking process-additional adsorption process-recrosslinking process <Micelle manufacturing process 2>
2 parts by mass of the amphiphilic block polymer compound 1 of Synthesis Example 2 and 6 parts by mass of S160 (trade name, manufactured by Degussa) as a coloring material were dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes. Thereafter, 90 parts by mass of distilled water was added to convert to an aqueous phase, and the pH was adjusted to 9 using an aqueous sodium hydroxide solution. Further, 0.05 parts by mass of azobisisobutyronitrile (AIBN) was added thereto, and tetrahydrofuran was removed by distillation under reduced pressure to obtain a dispersion composition.

<Crosslinking step 2>
Subsequently, the dispersion composition obtained in the micelle production step 2 was heated at a temperature of 60 ° C. for 48 hours to carry out a crosslinking reaction, thereby obtaining an intermicellar crosslinked dispersion composition. The progress of the crosslinking reaction was performed by identification of the double bond portion using ¹³ C-NMR.

<Additional adsorption process 2>
2 parts by mass of amphiphilic block polymer compound 1 of Synthesis Example 2 and 0.05 part by mass of azobisisobutyronitrile (AIBN) were dissolved in THF and added to the dispersion composition obtained in the crosslinking step 2. . After dispersing with an ultrasonic homogenizer for 10 minutes, the pH was adjusted to 9 using an aqueous sodium hydroxide solution. The dispersion composition was obtained by removing tetrahydrofuran by distillation under reduced pressure.

<Re-crosslinking step 2>
The dispersion composition obtained in the additional adsorption step 2 was heated at a temperature of 60 ° C. for 48 hours to carry out a crosslinking reaction, thereby obtaining a recrosslinked dispersion composition 2. The progress of the crosslinking reaction was evaluated by identification of the double bond portion using ¹³ C-NMR.

  Subsequently, using the obtained dispersion composition 2, an ink composition 2 was prepared so as to have the same composition as in Example 1.

(Comparative example 1) Micelle manufacturing process-crosslinking process <Micelle manufacturing process 3>
The following components were dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes.
-Hydrophobic polymer cross-linking agent of Synthesis Example 1 1.5 parts by mass-Amphiphilic block polymer compound 2 having a polymerizable unsaturated group at one end of Synthesis Example 4
4 parts by mass / coloring material (carbon black, trade name: S160, manufactured by Degussa) 6 parts by mass Thereafter, 90 parts by mass of distilled water is added to convert to an aqueous phase, and the pH is adjusted to 9 using an aqueous sodium hydroxide solution. It was adjusted. Further, 0.05 parts by mass of azobisisobutyronitrile (AIBN) was added thereto, and tetrahydrofuran was removed by distillation under reduced pressure to obtain a dispersion composition.

<Crosslinking step 3>
Subsequently, the dispersion composition obtained in the micelle production step 3 was heated at a temperature of 60 ° C. for 48 hours to carry out a crosslinking reaction, whereby an intermicellar crosslinked dispersion composition 3 was obtained. The progress of the crosslinking reaction was performed by identification of the double bond portion using ¹³ C-NMR.

  Subsequently, using the obtained dispersion composition 3, an ink composition 3 was prepared so as to have the same composition as in Example 1.

(Synthesis Example 5)
<Synthesis of polymer used in Comparative Example 2>
Polymerization was carried out as follows using a known group transfer polymerization.

A 1 l flask was equipped with a mechanical stirrer, thermometer, N ₂ inlet tube, outlet with drying tube and dropping funnel. Tetrahydrofuran (THF) 940 g and mesitylene 0.1 g were placed in the flask. Next, 230 μl of a 1.0 mol THF solution of tetrabutylammonium m-chlorobenzoate as a catalyst was added. Initiator 1-methoxy-1-trimethylsiloxy-2-methylpropene 1.5g (0.0086 mol) was injected.

  Next, 230 μl of a 1.0 mol THF solution of tetrabutylammonium m-chlorobenzoate was added over 130 minutes.

Thereafter, 151 g (0.86 mol) of benzyl methacrylate (BZMA) was added as an A block over 60 minutes. 30 minutes after polymerization progressed and 99 mol% or more of the monomers reacted, 212 g (0.86 mol) of ethoxytriethylene glycol methacrylate (ETEGMA) was added as a B block over 60 minutes. One hour after the polymerization progressed and 99 mol% or more of the monomers reacted, 27 g (0.17 mol) of trimethylsilyl methacrylic acid (TMS-MAA) was added as a C block over 60 minutes. After polymerization progressed and 99 mol% or more of the monomers reacted, a part of the solution was taken, and an aliquot of the solution was analyzed by ¹ H-NMR to confirm that no residual monomer was present. Thereafter, 50 ml of methanol was added and refluxed for 16 hours to remove the trimethylsilyl protecting group from methacrylic acid. Thereafter, the polymer was isolated by reprecipitation with hexane and dried using a vacuum dryer. As a result of NMR analysis, it was confirmed that the trimethylsilyl protecting group was completely removed.

  The block polymer was identified using NMR and GPC. Mn = 43800, Mw / Mn = 1.18, and the polymerization degree ratio was A: B: C = 100: 100: 20.

  Furthermore, the block polymer whose side chain of C block is a carboxylic acid sodium salt was obtained by neutralizing with an equal amount of 1N sodium hydroxide and distilling off water.

(Comparative Example 2)
<Preparation of pigment dispersion>
6 parts by mass of the block polymer compound of Synthesis Example 5 and 4 parts by mass of S160 (trade name, manufactured by Degussa) as a coloring material were dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes. Thereafter, 90 parts by mass of distilled water was added to convert to an aqueous phase, and the pH was adjusted to 9 using an aqueous sodium hydroxide solution. Dispersion composition 4 was obtained by removing tetrahydrofuran by distillation under reduced pressure.

  Subsequently, using the obtained dispersion composition 4, an ink composition 4 was prepared so as to have the same composition as in Example 1.

(Synthesis Example 6)
<Synthesis of polymer used in Comparative Example 3>
Prepared an automatic polymerization reactor (trade name: Polymerization Tester DSL-2AS type, manufactured by Sakai Sangyo Co., Ltd.) having a reaction vessel equipped with a stirring device, a dropping device, a temperature sensor, and a reflux device having a nitrogen introducing device at the top. did. Then, 1400 parts of methyl ethyl ketone was charged into the reaction vessel, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while maintaining the inside of the reaction vessel in a nitrogen atmosphere, and then a mixed solution in which the following components were mixed from a dropping device was dropped over 4 hours.
・ Butyl methacrylate 106 mass parts ・ N-butyl acrylate 312 mass parts ・ 2-hydroxyethyl methacrylate 75 mass parts ・ Methacrylic acid 307 mass parts ・ Styrene 200 mass parts ・ Perbutyl O (trade name) 140 mass parts (Active ingredient: t-butyl peroxy 2-ethylhexanoate, manufactured by NOF Corporation)
After completion of the dropwise addition, the reaction was further continued at the same temperature for 15 hours to obtain a solution of an anionic group-containing organic polymer compound (A) having an acid value of 200 and a weight average molecular weight of 48,000.

(Synthesis Example 7)
<Synthesis of polymer used in Comparative Example 3>
940 parts of methyl ethyl ketone was charged into the reaction vessel of the automatic polymerization reactor used in Synthesis Example 6, and the inside of the reaction vessel was purged with nitrogen while stirring. The temperature was raised to 80 ° C. while keeping the inside of the reaction vessel in a nitrogen atmosphere, and then a mixed solution of the following components was dropped from a dropping device over 4 hours.
・ Butyl acrylate 500 mass parts ・ Styrene 200 mass parts ・ Methacrylic acid 2,3-epoxypropyl 300 mass parts ・ V59 (trade name, active ingredient: 2,2′-azobis (2-methylbutyronitrile), sum After the completion of the dropwise addition of the solution in which 60 parts of Mitsui Chemicals were dissolved in 150 parts of methyl ethyl ketone, the reaction was further continued at the same temperature for 15 hours to obtain a solution of a glycidyl group-containing organic polymer compound (B) having a weight average molecular weight of 21,000. .

(Comparative Example 3)
Synthesis Example 6 The polymer compound (A) obtained in Synthesis Example 7 and the polymer compound (B) obtained in Synthesis Example 7 were blended immediately before dispersion in an amount of A: B = 9: 1 in terms of solid content in terms of mass. The molar equivalent of glycidyl group in 1000 g of the mixture before dispersion crosslinking was about 0.09.

  S160 (trade name, manufactured by Degussa), which is the blended polymer compound, 20% aqueous sodium hydroxide, water, and carbon black, was charged into a mixing tank equipped with a cooling jacket, and stirred and mixed. Here, the amount charged is 6 parts by mass of carbon black and the amount of the blended polymer is 4% by mass with respect to the carbon black in terms of solid content concentration. Further, the 20% aqueous sodium hydroxide solution is an amount by which the acid value of the anionic group-containing organic polymer compound is neutralized by 100%, and water is the amount necessary to bring the solid content concentration of the mixed solution to 30% by mass. .

After the mixed solution is dispersed for 10 minutes with a homogenizer, the mixed solution is passed through a dispersing device (trade name: SC mill SC100 / 32 type, manufactured by Mitsui Mining Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm. Dispersed for 4 hours. The number of revolutions of the dispersion device was 2700 revolutions / minute, and the dispersion temperature was kept at 40 ° C. or less through the cooling jacket through cold water.
The dispersion stock solution was extracted from the mixing tank, and then the mixing tank and the dispersion apparatus flow path were washed with 60 parts by mass of water, and the diluted dispersion liquid was obtained together with the dispersion stock solution. Methyl ethyl ketone was removed from the obtained diluted dispersion by distillation under reduced pressure.

  After cooling the dispersion from which methyl ethyl ketone had been removed, 10% hydrochloric acid was added dropwise with stirring to adjust the pH to 4.5, and the solid content was filtered and washed with water. Take the cake in a container, add 20% potassium hydroxide aqueous solution and water in an amount that neutralizes the acid value of the anionic group-containing organic polymer compound 90%, and add a dispersion stirrer (trade name: TK Homodispa Model 20, Special Machine It was dispersed again by Kagaku Kogyo Co., Ltd.). Thereafter, pure water was added to obtain a dispersion composition 5 having a solid content concentration of 10% by mass.

  Subsequently, using the obtained dispersion composition 5, an ink composition 5 was prepared so as to have the same composition as in Example 1.

[Evaluation]
The following evaluation was performed using the dispersion compositions or ink compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3.

(1) Measurement of adsorbed polymer amount The amount of polymer adsorbed to the colorant was calculated by measuring the obtained dispersion composition using a capillary type particle size distribution analyzer (trade name: CHDF2000, manufactured by Matec). The calculation method was calculated as the amount of adsorbed polymer with respect to the charged amount of the polymer compound.

  As is clear from Table 1, the dispersion compositions 1 and 2 of Examples 1 and 2 are compared with the dispersion compositions 3 to 5 of Comparative Examples 1 to 3, particularly the dispersion composition 4 of Comparative Example 2. Thus, it can be seen that the amount of the polymer adsorbed on the coloring material is increased.

(2) Filterability evaluation In order to confirm that the crosslinking reaction was not performed between micelles, the following filterability evaluation was performed. 20 mL of each ink composition was taken and subjected to pressure filtration using a membrane filter (Millipore, trade name: AP20). Thereafter, the filter was washed with pure water three times to wash the filter. It was visually examined whether coarse particles remained on the filter after filtration. When coarse particles remain, discoloration occurs due to clogging of the color material on the filter. If the filter does not change color, it is suggested that coarse particles due to crosslinking between micelles are not generated. The filter discoloration also occurs when coarse particles are generated due to aggregation.

  The evaluation results are shown in Table 1 with ○ indicating that there was no discoloration and × indicating that discoloration was observed.

  As is clear from Table 1, regarding the ink compositions of Examples 1 and 2 and Comparative Examples 1 and 2, no discoloration of the filter was observed, and coarse particles could not be confirmed. On the other hand, discoloration was observed in the filter obtained by filtering the ink composition 5 of Comparative Example 3.

(3) Stability evaluation with a solvent In order to confirm whether the crosslinking reaction has proceeded sufficiently and the polymer is crosslinked on the surface of the colorant, the following is given to each dispersion composition before filtration. Solvent stability tests were performed. 250 parts by mass of THF was added to 25 parts by mass of each ink composition, and dispersed for 10 minutes with an ultrasonic homogenizer. Thereafter, THF was removed with a dialysis membrane (trade name: molecular porous membrane tube (MWCO: 3500), manufactured by SPECTRU Laboratories), and the solid content concentration was adjusted again to 20% by mass. Using this dispersion, a solvent was added again to obtain an ink composition, which was then transferred to a Teflon (registered trademark) container and stored in an environment at 60 ° C. for 2 months. Then, the precipitation state was examined visually.

  The evaluation results are shown in Table 1 as “◯” when no precipitation was observed and “X” when precipitation was observed.

  In any of the ink compositions 1 to 3 of Examples 1 and 2 and Comparative Example 1, no precipitation was observed, the crosslinking reaction was sufficiently advanced, and the polymer was crosslinked on the color material surface layer. confirmed.

(4) Ejection stability evaluation Canon ink jet printers (trade name: BJ F930) for ink compositions 1 to 3 of Examples 1 and 2 and Comparative Example 1 which were excellent in filterability evaluation and solvent stability evaluation ) Was used to conduct a discharge stability test. As a result, it was confirmed that any of the ink compositions was able to confirm the ejection of ink droplets and had sufficient ejection performance. Further, when 5 sheets of solid printing were continuously performed on A4 paper, any ink composition could be printed without fading. Furthermore, when 5 sheets of solid printing were additionally printed continuously on A4 paper, the ink compositions 1 and 2 obtained in Examples 1 and 2 were able to print without fading, but were obtained in Comparative Example 1. In the ink composition, slight fading was observed.

  As described above, the present invention can provide a method for producing a dispersion composition having sufficient dispersibility by having a micelle production process, a crosslinking process, and an additional adsorption process.

  The production method according to the present invention can be used particularly for the production of compositions useful as various ink-jet inks.

It is a schematic diagram of the micelle structure obtained by the micelle manufacturing process of the present invention. It is a schematic diagram of the micelle structure obtained by the crosslinking step of the present invention. It is a schematic diagram of the micelle structure obtained by the additional adsorption process of the present invention.

Explanation of symbols

10 Dispersion (enlarged view)
14 Hydrophobic substance 15a Crosslinker or polymerization initiator 15b Crosslinkage 20 First amphiphilic block polymer compound 21 Hydrophobic block segment 22 of first amphiphilic block polymer compound First amphiphilic block polymer compound Hydrophilic block segment 20 'Second amphiphilic block polymer compound 21' Hydrophobic block segment 22 'of second amphiphilic block polymer compound Hydrophilic block segment of second amphiphilic block polymer compound

Claims (17)

  A first amphiphilic block polymer compound having a hydrophobic block segment and a hydrophilic block segment and having a crosslinkable functional group, and encapsulated in a micelle formed by the first amphiphilic block polymer compound A method for producing a composition comprising a hydrophobic substance and an aqueous solvent, wherein a micelle is formed by adsorbing a hydrophobic block segment of the first amphiphilic block polymer compound to the hydrophobic substance. A second amphiphilic block polymer comprising a manufacturing step, a crosslinking step of crosslinking the first amphiphilic block polymer compound in the micelle, and a hydrophobic block segment and a hydrophilic block segment after the crosslinking step Production of a composition comprising at least an additional adsorption step for adsorbing a compound to the hydrophobic substance Law.   The method for producing a composition according to claim 1, wherein the second amphiphilic block polymer has a crosslinkable functional group.   3. The method for producing a composition according to claim 2, further comprising a re-crosslinking step of causing the second amphiphilic block polymer compound to undergo a crosslinking reaction in the micelle after the additional adsorption step.   The method for producing a composition according to claim 3, wherein the additional adsorption step and the recrosslinking step are repeated twice or more.   The first amphiphilic block polymer compound has a crosslinkable functional group only in the hydrophobic block segment, and is crosslinked by the crosslinkable functional group. A method for producing the composition described.   The method for producing a composition according to any one of claims 1 to 5, wherein the crosslinkable functional group is a self-crosslinkable functional group.   The method for producing a composition according to claim 6, wherein the self-crosslinkable functional group is a radically polymerizable unsaturated group or a hydrolyzable alkoxysilane group.   The method for producing a composition according to any one of claims 1 to 5, further comprising a crosslinking agent that causes the crosslinking functional group to undergo a crosslinking reaction.   The method for producing a composition according to claim 8, wherein the crosslinking agent is a hydrophobic compound.   The method for producing a composition according to claim 9, wherein the hydrophobic compound is a polymer compound.   11. The first amphiphilic block polymer compound comprises an ionic hydrophilic block segment and a nonionic hydrophilic block segment as hydrophilic block segments. A method for producing the composition described.   The first amphiphilic block polymer compound is bonded in the order of the hydrophobic block segment, the nonionic hydrophilic block segment, and the ionic hydrophilic block segment. A method for producing the composition.   The method for producing a composition according to any one of claims 1 to 12, wherein the main chain structure of the first amphiphilic block polymer compound is a polyalkenyl ether structure in any segment.   The method for producing a composition according to claim 1, wherein the hydrophobic substance is a color material.   The method for producing a composition according to claim 14, wherein the colorant is a pigment.   A composition produced by the production method according to claim 1.   A liquid application method comprising a step of recording an image by applying the composition according to claim 16 to a medium.

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