JP2008088366A - Method for producing composition containing polymer compound, composition, image forming method and image forming apparatus - Google Patents

Abstract

Disclosed is a composition having excellent glossiness and fastness and having excellent dispersion stability.
A block copolymer compound having at least a hydrophilic block segment having a crosslinkable functional group and having both ends of a hydrophobic block segment and a non-crosslinkable hydrophilic block segment, a hydrophobic substance, and an aqueous solvent And a step of forming a micelle by adsorbing the block copolymer compound to the hydrophobic substance at the hydrophobic block segment in the aqueous solvent, and the non-existence of the micelle formed in the aqueous solvent. And a step of cross-linking the micelles by cross-linking the cross-linkable functional groups while suppressing cross-linking of the micelles by the steric hindrance action of the cross-linkable hydrophilic block segment. .
[Selection] Figure 2

Description

  The present invention relates to a method for producing a composition containing a block copolymer compound, for example, useful as various inkjet inks, the composition, an image forming method, and an image forming apparatus.

  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 problems, the use of pigment-dispersed inks has been studied (see Patent Document 1), and ink jet inks that actually use pigment inks are now widely used.

  A large number of pigments are used as colorants for ink jet recording inks and writing instrument inks because of excellent fastness such as water resistance and light resistance. Since pigments are not soluble in water, it is important to stably disperse pigments in water as fine particles when used in ink compositions. In general, an ink composition using such a pigment as a colorant is required to make the pigment easily wetted with water and prevent the pigment from settling. From that viewpoint, a pigment dispersion is prepared by dispersing a mixture of a pigment, a liquid medium, and a dispersant with a disperser or the like, and various additives are added to the pigment dispersion as necessary. ing. As described above, when producing an ink composition, the pigment is often used in the state of a pigment dispersion, and particularly affects the characteristics of the ink composition. Has been developed.

  However, when an organic pigment or carbon black is used as the pigment ink, if the pigment is not very finely dispersed and stabilized, high definition and high color rendering properties may not be obtained as the ink. Furthermore, if the dispersion stability of the pigment is not excellent, nozzle clogging may occur easily. For this reason, among the ink jet recording methods, the thermal method, in particular, can provide a high-speed and high-quality printed matter, but it is preferable that the ink is excellent in dispersion stability and re-dissolvability because part of the ink is heated.

  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 is not sufficient in the ink composition obtained by preparing the conventional pigment dispersion. 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, a method of physically increasing dispersion stability by crosslinking the periphery of the pigment with a crosslinkable resin as described in Patent Document 2 has been used.
US Pat. No. 5,085,698 JP 2004-27156 A

  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. FIG. 6 is a model diagram showing a cross-linking configuration that is considered to occur in Patent Document 2. FIG. 6 shows a state in which the dispersions in which the pigment 1 is included by the dispersion resin 2 are bonded by the cross-linking portion 3. In FIG. 6, there are two dispersions that are crosslinked and bonded. However, when there are a large number of crosslinked bonds between the dispersions, it is considered that coarse particles are formed to cause the above phenomenon.

  Therefore, conventionally, in order to make full use of this contradictory performance, either performance was used in a balance that compromised, or a method such as purification by filtration or the like was used, so that sufficient effects due to crosslinking were obtained. It was not obtained or performance variation was observed.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition having excellent gloss and fastness and having excellent dispersion stability.

  In view of these situations, the present inventors have considered using cross-linking of the dispersion resin by a completely new approach. That is, by using an amphiphilic block copolymer dispersion as a dispersion resin, a system in which steric hindrance is formed around a coloring material that is a hydrophobic substance and cross-linking is performed only at an inner portion of the steric hindrance. It is.

  That is, the present invention includes at least a block copolymer compound having a hydrophilic block segment having a crosslinkable functional group and having both ends of a hydrophobic block segment and a non-crosslinkable hydrophilic block segment, a hydrophobic substance, An aqueous solvent, in which the block copolymer compound adsorbs to the hydrophobic substance on the hydrophobic block segment to form a micelle, and the micelle formed in the aqueous solvent. A step of cross-linking the micelles by cross-linking the cross-linkable functional groups while suppressing cross-linking of the micelles by the steric hindrance action of the non-cross-linkable hydrophilic block segment. A composition production method and a composition produced by the method.

  The present invention also provides a method for producing a composition, wherein the composition is an ink composition, and a composition produced by the method.

  The present invention also relates to a method for producing a composition, wherein the composition is an inkjet composition, and a composition produced by the method.

  The present invention also provides an image forming method comprising a step of recording an image by applying the ink composition or the ink jet composition to a medium.

  According to another aspect of the present invention, there is provided an image forming apparatus having means for recording an image by applying the ink composition or the ink jet composition to a medium.

  The present inventors refer to this crosslinked form as intramicellar crosslinking and distinguish it from conventional crosslinked forms.

  By adopting the intramicellar cross-linking structure as in the present invention, the cross-linking between micelles can be substantially ignored, and the cross-linking form can be achieved with the same molecular weight and viscosity as the conventional micelle structure without cross-linking. It can be achieved.

  According to the present invention as described above, it is possible to provide a composition that is excellent in glossiness and fastness and has excellent dispersion stability. The present invention can also provide an image forming method and an image forming apparatus using the above composition as an ink composition or an ink jet composition.

  Hereinafter, the composition of the present invention will be exemplified and described in detail with reference to the drawings.

  FIG. 1 is a schematic diagram showing the composition of the present invention, and FIG. 2 is a schematic diagram showing an example of the micelle structure of FIG.

  In FIG. 1, reference numeral 40 denotes a container. The aqueous solvent 30 is contained in the container 40 and the dispersion 10 is dispersed in the aqueous solvent 30. The dispersion 10 is composed of a hydrophobic substance 14 and a dispersion resin 20, and the dispersion resin 20 is arranged around the hydrophobic substance 14 so as to enclose the hydrophobic substance 14. The hydrophobic substance 14 maintains the dispersed state. The dispersion resin 20 is crosslinked by a method such as heating or irradiation with energy rays after the dispersion step in which the dispersion resin 20 is adsorbed to the hydrophobic substance 14 in the aqueous solvent 30 to form micelles. ing. As a result, the dispersion 10 is cross-linked inside the dispersion 10 to form a cross-linked portion 15.

  In order to describe the dispersion resin 10 in more detail, it will be described with reference to FIG. FIG. 3 shows an example in which an amphiphilic triblock copolymer is used as the dispersion resin.

  In FIG. 3, the hydrophobic substance 14 is a pigment, and the dispersion resin 20 is an amphiphilic block copolymer compound. The amphiphilic block copolymer compound 20 has a hydrophobic block segment 21 and a hydrophilic block segment 22. The hydrophilic block segment 22 is composed of a nonionic hydrophilic block segment 22a and an ionic hydrophilic block segment 22b. In an aqueous solvent, the amphiphilic triblock copolymer 20 is oriented so that the hydrophobic block segment 21 is on the inside, forming a micelle state. The pigment 14 is included in the core portion of the micelle so as to be included in the amphiphilic triblock copolymer 20, and the hydrophobic block segment 21 is adsorbed on the pigment 14. Further, the nonionic hydrophilic block segment 22a is provided with a crosslinkable functional group (not shown), and this crosslinkable functional group is a crosslinkable functional group of another nonionic hydrophilic block segment 22a. And a cross-linking portion 15 bonded to the. Each block segment may be composed of a single component as shown in FIG. 5 (a), or may be a copolymer composed of two or more components as shown in FIG. 5 (b) (FIG. 5 (b). ) Illustrates a copolymer in which the nonionic hydrophilic block segment 22a is composed of two components). The copolymer constitutes block segments with a random or gradient structure. In addition, the crosslinkable hydrophilic block segment made of the copolymer exemplified in FIG. 5B has a crosslinkable functional group in at least one of the components 22a ′ and 22a ″.

  In the present invention, the cross-linking portion 15 is substantially expressed only in the non-terminal block segment, and this configuration forms a cross-linked structure in micelles. For example, it can be realized by providing a crosslinkable functional group only in the nonionic hydrophilic block segment 22a of the amphiphilic block copolymer 20. In this way, while allowing cross-linking of polymers in the same micelle, cross-linking of other micelles causes the ionic hydrophilic block segment 22b to be sterically hindered in an aqueous solvent and inhibit the binding. .

  Therefore, in the configuration of the present invention, it is possible to prevent the increase in viscosity and variation in the cross-linked state resulting from the binding between micelles, which is a conventional demerit, and to the dispersion resin pigment, which is a merit brought about by the cross-linking. Strong fixation can be obtained. Thereby, for example, even when the composition is subjected to a strong impact or the composition is exposed to a high heat atmosphere such as thermal ink jet, the dispersed state can be made good. It is also possible to improve the discharge performance.

  Furthermore, this cross-linking does not release the dispersion resin even on the media, greatly reducing the chances of the pigment being exposed to the media surface compared to conventional methods and contributing to improved glossiness and fastness. Conceivable.

  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.

  The block copolymer compound included in the composition of the present invention is an amphiphilic block copolymer compound. Amphiphilic means that it has both amphiphilic and lyophobic properties, and amphiphilic block copolymer compound is a polymer that has at least one or more amphiphilic and lyophobic block segments. A compound. The above-mentioned amphiphilic property represents a property of having a large affinity for a main solvent used in a polymer-containing composition described later, and the lyophobic property is a property of a low affinity for a solvent. . Since the solvent of the composition of the present invention is an aqueous solvent and the main solvent is water, the block copolymer compound of the present invention has at least one or more hydrophilic and hydrophobic block segments.

  The block copolymer compound of the present invention preferably has a crosslinkable functional group composed of a polymerizable unsaturated group, and the crosslinkable functional group is provided only in the hydrophilic block segment. It is what.

  The micelle of the present invention refers to a core-shell type micelle obtained by dispersing an amphiphilic block copolymer having both a hydrophilic block segment and a hydrophobic block segment in an aqueous solvent. At this time, the micelle structure of the present invention shows a structure in which the hydrophobic block segment faces the inside and the hydrophilic block segment faces the outside. As described above, the core-shell type micelle in which the hydrophobic part is the core and the hydrophilic part is the shell, the hydrophobic core is covered with the hydrophilic shell part. Although it is generally thought that the structure is less susceptible to the effects of, the details are not clear.

  The micelle structure of the present invention forms a dispersion containing a hydrophobic substance. The dispersion containing the hydrophobic substance is preferably a polymer microsphere. 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 copolymer compound, and the coloring material is encapsulated with the polymer, depending on the temperature. A method for examining the change of the dispersion state is mentioned. Or it can confirm that it is included by observing a composition with an electron microscope.

  Further, by disposing a crosslinkable hydrophilic block segment other than the polymer terminal site, crosslinking between the dispersions can be prevented even when the crosslinkable functional group is crosslinked. Thus, the present invention is characterized in that the phenomenon of increase in coarse particles or viscosity, which has occurred in the conventional method for crosslinking a dispersion, is less likely to occur.

  As a preferable cross-linked structure of the dispersion contained in the composition of the present invention, a structure as shown in FIG. 4 can be exemplified. This structure is a functionally separated structure of a hydrophobic block segment that adsorbs to a hydrophobic substance, a hydrophilic block segment having a crosslinkable functional group on the outside thereof, and a hydrophilic block segment having dispersibility. This structure can be said to be a preferable structure because the mobility of the cross-linked portion is good and an efficient cross-linking reaction can be performed.

  Such a configuration can also be achieved by making the structure of the block copolymer compound as shown in FIG. 5 (a) or (b).

  In the present application, the term “crosslinked” means that the crosslinkable functional group contained in the hydrophilic block segment is crosslinked by a crosslinking reaction. As the crosslinkable functional group, 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 (in particular, a self-crosslinkable functional group) There is).

  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. Of these, amino groups, hydroxyl groups, and carboxyl groups are preferred because of their high reactivity and easy introduction into the 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 two or more radically polymerizable unsaturated groups and a compound having two or more hydrolyzable alkoxysilane groups can be partially used in combination.

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

  The crosslinkable functional group contained in the hydrophilic block segment of the block copolymer compound of the present invention preferably does not inhibit the hydrophilicity of the hydrophilic block segment. Specific examples of the crosslinkable functional group include polymerizable unsaturated groups such as isocyanate and epoxy.

  The block copolymer compound contained in the composition of the present invention is an amphiphilic block copolymer compound in which at least one block segment is hydrophobic and at least one block segment is hydrophilic. The hydrophilicity is a property that has a high affinity for water and is easily dissolved in water, and the hydrophobic property is a property that has a low affinity for water and is difficult to dissolve in water.

  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 in the block copolymer compound contained in the ink composition of the present invention is not limited to these.

  Moreover, as a hydrophobic block segment, the block segment containing the repeating unit structure which has hydrophobic units, such as an isobutyl group, t-butyl group, a phenyl group, a biphenyl group, a naphthyl group, is mentioned, for example. As a specific example, it is a block segment having a hydrophobic monomer such as styrene or t-butyl methacrylate as a repeating unit, but the hydrophobic block in the block copolymer compound contained in the composition of the present invention is not limited thereto. .

  Moreover, the preferable form of the block copolymer compound contained in the composition of this invention is described. The block copolymer compound of the present invention has three or more block segments, and the main chain structure of each block segment is preferably a polyalkenyl ether structure. Having a vinyl ether repeating unit structure is extremely useful in that it can provide a polymer material with low viscosity and good dispersibility.

  More preferably, it has two or more hydrophilic block segments each consisting of a nonionic hydrophilic group and an ionic hydrophilic group. Or it is preferable to have a nonionic hydrophilic block segment and an ionic hydrophilic block segment as a 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 a composition excellent in ejection performance particularly in the thermal ink jet method is obtained.

  Each block segment of the block copolymer compound contained in the composition of the present invention may be composed of repeating units derived from a single monomer, or may have a structure having repeating units 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 block copolymer compound of the present invention may be a polymer in which the above block copolymer is graft-bonded to another polymer.

  Moreover, it is possible to exhibit two or more functions by having three or more block segments. For this reason, it is possible to form a higher-order and precise structure than a polymer compound composed of two block segments. In addition, by maintaining a property similar to a plurality of block segments, it is possible to make the property more stable.

  That is, the block copolymer compound contained in the composition of the present invention is more preferably a block copolymer having a main chain structure of a polyalkenyl ether structure and having three or more block segments. By having more than two block segments, more functions can be separated.

  Preferable examples of the block copolymer compound contained in the composition of the present invention include a block copolymer compound which is an ABC type triblock copolymer composed of three different block segments ABC. The ABC type triblock copolymer in which the A block is a hydrophobic block segment, the B block is a nonionic hydrophilic block segment, and the C block is an ionic hydrophilic block segment is described below.

  The nonionic hydrophilic block segment corresponding to the B block may be only a repeating unit structure having a nonionic crosslinkable functional group. Nonionic having a crosslinkable functional group, preferably comprising a copolymer of a repeating unit structure that is nonionic and has a crosslinkable functional group, and a repeating unit structure that is nonionic and has no crosslinkable functional group It is a hydrophilic block segment. By using a copolymer, it is possible to appropriately adjust the hydrophilicity and crosslinking reactivity of the nonionic hydrophilic block segment having a crosslinkable functional group. Also, during the crosslinking reaction, the hydrophilicity is improved by copolymerization, and a contribution to the progress of the crosslinking reaction in a uniform liquid phase system can be expected. Examples of the copolymer include a random copolymer, a block copolymer, and a gradient (gradient type) copolymer.

  In the composition of the present invention, the content of the repeating unit structure having a crosslinkable functional group contained in the nonionic hydrophilic block segment of the block copolymer compound is based on the whole nonionic hydrophilic block segment. 1 to 90 mol% is preferable. More preferably, it is the range of 5-80 mol%. If the amount is less than 1 mol%, crosslinking may be insufficient and the fastness may be deteriorated. If the amount exceeds 90 mol%, interaction with the coloring material is unlikely to occur, and it may be difficult to enclose the coloring material before the crosslinking reaction. Therefore, it is not preferable.

  Next, a specific repeating unit structure of an ABC type triblock copolymer compound that is particularly preferably used in the present invention with respect to a block copolymer compound comprising a hydrophobic block segment and a hydrophilic block segment and capable of crosslinking with the hydrophilic block segment is exemplified below. .

  The hydrophobic block segment corresponding to the A block is preferably a block segment having a repeating unit structure composed of a polyalkenyl ether structure. Specific examples include a repeating unit structure represented by the following general formula (1) or the following general formula (2), but the hydrophobic block segment in the block copolymer compound of the present invention is not limited thereto.

In general formula (1), A represents an optionally substituted polyalkenyl ether group. The polyalkenyl ether group may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, or a halogen atom. B represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. Examples of the substituent for the alkylene group include ethylene, propylene, butylene and the like. m represents an integer of 0 to 30, preferably 1 to 10. When m is 2 or more, each B may be different. D represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene and the like. E represents either an aromatic ring that may be substituted, a structure in which up to three aromatic rings that may be substituted are bonded by a single bond, or a methylene group. Examples of the aromatic ring structure include phenyl, pyridylene, pyrimidyl, naphthyl, anthranyl, phenanthranyl, thiophenyl, furanyl and the like. R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms, which may be substituted, or an aromatic ring which may be substituted. Examples of the aromatic ring structure include a phenyl group, a pyridyl group, and a biphenyl group. Examples of the substituent include an alkyl group and an alkoxy group. Further, a hydrogen atom not substituted with R ¹ in either the aromatic ring or the methylene group may be substituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom.

In general formula (2), A represents a polyalkenyl ether group which may be substituted. The alkylene group constituting the polyalkenyl ether group may be substituted with a linear or branched alkylene group having 1 to 5 carbon atoms, or a halogen atom. B ₁ represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. Examples of the substituent for the alkylene group include ethylene, propylene, butylene and the like. m represents an integer of 0 to 30, preferably 1 to 10. When m is 2 or more, each B may be different. J is a linear bond or a branched alkyl group having 3 to 15 carbon atoms, an optionally substituted aromatic ring, or an optionally substituted aromatic ring having a single bond Represents any one of up to three bonded structures. Examples of the alkyl group include a propyl group, an isopropyl group, a butyl group, and a t-butyl group. Examples of the aromatic ring structure include a phenyl group, a naphthyl group, a pyridyl group, and a biphenyl group. Examples of the substituent include an alkyl group and an alkoxy group.

  As a specific example of the repeating unit structure that becomes a hydrophobic block, for example,

However, it is not limited to these.

  Next, although the case where the nonionic hydrophilic block segment which has a crosslinkable functional group is used for B segment is demonstrated below as an example, it is not limited to this. As described above, the nonionic hydrophilic block segment having a crosslinkable functional group may be composed of a single repeating unit structure, or may be composed of a repeating unit structure of two or more components. It is also possible to use an ionic hydrophilic block segment containing a repeating unit structure having an organic acid such as carboxylic acid or a salt thereof as a substituent or a side chain, but here a nonionic hydrophilic block is used. The segment will be described in detail as a preferred example.

  The nonionic hydrophilic block segment may be composed of only a repeating unit structure having a structure having a crosslinkable functional group in its substituent or side chain, such as an amino group or a hydroxyl group. Moreover, the copolymer of the repeating unit structure which has a crosslinkable functional group, and the nonionic hydrophilic repeating unit structure which has a polyoxyethylene chain may be sufficient. A specific example is a block segment having a monomer such as polyvinyl alcohol as a repeating unit, and a block segment having a repeating unit structure composed of a polyalkenyl ether structure is preferable. Moreover, the hydrophilic block segment which has a crosslinkable functional group can also be formed by copolymerizing what has self-crosslinkability as a crosslinkable functional group.

  Specific examples thereof include a copolymer block segment having a repeating unit structure represented by the following general formula (3) and a repeating unit structure having a crosslinkable functional group described later. However, the nonionic hydrophilic block segment having a crosslinkable functional group in the block copolymer compound of the present invention is not limited thereto.

  In general formula (3), A represents an optionally substituted polyalkenyl ether group. The alkenyl group constituting the polyalkenyl ether group may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, or a halogen atom. B 'represents a linear or branched alkylene group having 1 to 5 carbon atoms which may be substituted. A linear alkylene group having 1 to 2 carbon atoms is preferred. Examples of the substituent for the alkylene group include methylene, ethylene, propylene and the like. m represents an integer of 0 to 30, preferably 1 to 10. When m is 2 or more, each B 'may be different. D 'represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms which may be substituted. Examples of the alkylene group include methylene, ethylene, propylene and the like. K represents either a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted, or a hydroxyl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

The repeating unit structure represented by the general formula (3) exhibits hydrophilicity. Therefore, the above structure includes a case where the unit unit is hydrophilic such as an oxyethylene group or a hydroxyl group, and a case where it is hydrophobic such as an oxypropylene group, an ethyl group or a propyl group. In this case, the whole must be hydrophilic. For example, when K is a propyl group (B′O) _m is a somewhat long oxyethylene group, and when K is a hydroxyl group, (B′O) _m Becomes an oxypropylene group. As a specific example of the repeating unit structure that becomes a nonionic hydrophilic block, for example,

However, it is not limited to these.

  By copolymerizing the nonionic repeating unit structure and the repeating unit structure having a crosslinkable functional group exemplified below, a nonionic hydrophilic block segment having a crosslinkable functional group can be formed. Specific examples of the repeating unit structure having the crosslinkable functional group are shown below.

  Among the specific examples of the repeating unit structure having a crosslinkable functional group exemplified above, the above three examples have a hydroxyl group and an amino group, and can themselves be a nonionic hydrophilic block. is there. The lower two examples are examples having self-crosslinking ability.

  Moreover, as C block which is an ionic hydrophilic block segment, the block segment containing the repeating unit structure which has carboxylic acid, carboxylate, etc. is mentioned, for example. A block segment having a repeating unit structure composed of a polyalkenyl ether structure is preferred. Specific examples include a repeating unit structure represented by the following general formula (4), but the ionic hydrophilic block in the polymer compound of the present invention is not limited thereto.

In General Formula (4), A represents an optionally substituted polyalkenyl ether group. The polyalkenyl ether group may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, or a halogen atom. B ″ represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted. Examples of the substituent of the alkylene group include ethylene, propylene, butylene and the like. Represents an integer from 0 to 30, preferably from 1 to 10. When m is 2 or more, each B ″ may be different. D ″ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, Examples include butylene, octylene, etc. E ″ is either an optionally substituted aromatic ring, or a structure in which up to three optionally substituted aromatic rings are bonded by a single bond, or a methylene group. Represents. Examples of the aromatic ring structure include phenyl, pyridylene, pyrimidyl, naphthyl, anthranyl, phenanthranyl, thiophenyl, furanyl and the like. R ² represents a structure of —COO ⁻ M. M represents a monovalent or polyvalent metal cation. Specific examples of M include sodium, potassium, lithium and the like as monovalent metal cations, and magnesium, calcium, nickel, iron and the like as polyvalent metal cations. When M is a polyvalent metal cation, M forms a counter ion with two or more of the anions COO ⁻ . A hydrogen atom not substituted with R ² in either the aromatic ring or the methylene group may be substituted. Examples of the substituent include an alkyl group, an alkoxy group, and a halogen atom. Preferably, an aromatic carboxylic acid derivative having a carboxylic acid group bonded to an aromatic carbon is present in the side chain of the C segment.

  As a specific example of the repeating unit structure that becomes an ionic hydrophilic block, for example,

However, it is not limited to these.

  The content of the hydrophobic block segment contained in the block copolymer compound in the present invention is 5 to 95% by mass, preferably 10 to 90% by mass. Moreover, content of a hydrophilic block segment is 5-95 mass%, Preferably it is the range of 10-90 mass%.

  When the block copolymer compound is an ABC type triblock copolymer compound, the content of the hydrophobic block segment A in the block segment ABC is in the range of 5 to 94 mass%, preferably 5 to 89 mass%. The content of the nonionic hydrophilic block segment B is 5 to 94% by mass, preferably 10 to 90% by mass. The content of the ionic hydrophilic block segment C is 1 to 90% by mass, preferably 1 to 80% by mass.

  The number average molecular weight (Mn) of the block copolymer compound contained in the composition of the present invention is preferably 500 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 500, the steric effect as a polymer may be difficult to obtain due to the low molecular weight. The preferable polymerization degree of each block segment is 3 or more and 10,000 or less independently. More preferably, it is 3 or more and 5000 or less. More preferably, it is 3 or more and 4000 or less.

The polymerization of the block copolymer compound contained in the composition of the present invention is often carried out mainly by cationic polymerization. Examples of the initiator include proton acids 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 Examples include a combination of a Lewis acid such as _1.5 AlCl _1.5 (R represents alkyl) and a cation source (the cation source includes an adduct of proton acid, water, alcohol, vinyl ether and carboxylic acid, etc.). By causing these initiators to coexist with a polymerizable compound (monomer), a polymerization reaction proceeds and a block copolymer 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 copolymers, 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 block copolymer compound contained in the composition of the present invention is used in the range of 0.1% by mass to 90% by mass. Preferably they are 1 mass% or more and 80 mass% or less. For an inkjet printer, it is preferably used in an amount of 1 to 30% by mass.

  Next, the hydrophobic substance contained in the composition of 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 pigments, metal particles, organic fine particles, inorganic fine particles, magnetic particles, organic semiconductors, conductive materials, optical materials, nonlinear optical materials, and the like. However, it is not limited to these as long as it exhibits the function even if it is included in the dispersion resin.

  The hydrophobic substance contained in the composition of 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 used in the 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 addition, a newly synthesized pigment may be used for the present invention.

  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.

  The pigment used in the composition of the present invention is preferably 0.1 to 50% by mass relative to the mass of the composition. When the amount of the pigment is 0.1% by mass or more, a preferable image density is obtained, and when it is 50% by mass or less, the pigment exhibits a preferable dispersibility. A more preferable range is 0.5 to 30% by mass.

  A dye can also be used in the ink composition of the present invention. Oil-soluble dyes as described below or dispersible dye insoluble pigments can be used.

  Examples of oil-soluble dyes include commercial products of each color below.

  Examples of black oil-soluble dyes include C.I. I. Solvent Black-3, -22: 1, -50, etc. are mentioned, but it is not limited to these.

  Examples of yellow oil-soluble dyes include C.I. I. Solvent Yellow-1, -25: 1, -172 etc. are mentioned, However, It is not limited to these.

  Examples of orange oil-soluble dyes include C.I. I. Solvent Orange-1, -40: 1, -99 etc. are mentioned, However, It is not limited to these.

  Examples of red oil-soluble dyes include C.I. I. Solvent Red-1, -111, -229, etc. are mentioned, but it is not limited to these.

  Violet oil-soluble dyes include C.I. I. Solvent Violet-2, -11, -47 etc. are mentioned, However, It is not limited to these.

  Examples of blue oil-soluble dyes include C.I. I. Solvent Blue-2, -43, -134 etc. are mentioned, However, It is not limited to these.

  Green oil-soluble dyes include C.I. I. Solvent Green-1, -20, -33 etc. are mentioned, However, It is not limited to these.

  Examples of brown oil-soluble dyes include C.I. I. Solvent Brown-1, -12, -58 etc. are mentioned, However, It is not limited to these.

  The dye used in the composition of the present invention is preferably 0.1 to 50% by mass relative to the mass of the composition.

  These examples of the hydrophobic substance are preferable for the composition of the present invention, but the hydrophobic substance used in the composition of the present invention is not particularly limited to the hydrophobic substance. . 0.1-50 mass% is preferable with respect to the mass of a composition, and, as for the hydrophobic substance used for the composition of this invention, 0.5-30 mass% is more preferable.

  Components other than the polymer compound and hydrophobic substance contained in the composition of the present invention will be described in detail. Other components include aqueous solvents, additives, crosslinkers and the like.

[Aqueous solvent]
The aqueous solvent referred to in the present invention is mainly composed of water, and contains an organic solvent or an aqueous solvent in addition to water as long as the polymer compound and the hydrophobic substance are dispersed in a micelle state. It does not matter. The water contained in the present invention is preferably ion-exchanged water, pure water, or ultrapure water from which metal ions have been removed. Examples of the organic solvent include hydrocarbon solvents, aromatic solvents, ether solvents, ketone solvents, ester solvents, amide solvents, and the like. 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 the composition of the present invention, the content of the aqueous solvent is preferably in the range of 9.90 to 95% by mass with respect to the total mass of the composition. More preferably, it is the range of 19.5-90 mass%.

[Additive]
Various additives, auxiliaries and the like can be added to the composition of the present invention as necessary. One additive is a dispersion stabilizer that stably disperses a pigment in a solvent. The composition of the present invention has a function of dispersing a particulate solid such as a pigment by a polymer containing a polyvinyl ether structure, but when the dispersion is insufficient, another dispersion stabilizer is added. May be.

  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.

[Crosslinking agent]
In the composition of the present invention, a cross-linking agent selected by a combination of the cross-linkable functional group and the cross-linking agent described above can be added depending on the type of cross-linkable functional group to be used. The cross-linking agent is added before or after the hydrophobic substance is dispersed. The period is more preferably before dispersion because the probability that a crosslinking agent is present on the surface of the hydrophobic substance is high.

  Crosslinking of the block copolymer compound in the present invention is performed as follows. First, the block copolymer compound and the pigment are dispersed in water and, if necessary, an aqueous solvent composed of a water-soluble organic solvent or the like. 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, the concentration is adjusted by adding water or the like in advance, and is preferably set to a range of 20% by mass or less, more preferably 0.1 to 10% by mass.

  Crosslinking by a carboxyl group and an epoxy group, crosslinking by a hydroxyl group and an N-alkoxymethylamide group, crosslinking by a hydrolyzable alkoxysilane group, crosslinking by an amino group and an isocyanate group, etc., for example, 50 to 150 ° C. under normal pressure or pressure. And crosslinking by heating at. In this case, it is also recommended to use a catalyst. In the case where the reaction is carried out in an aqueous solvent, it is also preferable to use a block isocyanate derivative as a crosslinking material.

  In the case of 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 a redox system at a temperature of about 50 to 90 ° C. It can be cross-linked.

  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 composition of the present invention is preferably a hydrophilic compound or an amphiphilic compound. The cross-linking agent used in the composition of the present invention is preferably hydrophilic because the cross-linkable functional group of the polymer compound is contained in the hydrophilic block segment, but a lipophilic or water-dispersible one should be used. You can also.

  Moreover, it is preferable that the crosslinking agent contained in the composition of this invention is a polymer compound.

  The blending ratio of the block copolymer 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 content mass ratio.

Next, the manufacturing method of the composition of this invention is demonstrated in detail. The composition of the present invention has the following steps.
A block copolymer compound, a hydrophobic substance, and an aqueous solvent are prepared, and the block copolymer compound adsorbs to the hydrophobic substance at the hydrophobic block segment in the aqueous solvent to form micelles. Process.
-Cross-linking the micelles by cross-linking the cross-linkable functional groups while suppressing cross-linking of the micelles by the steric hindrance of the non-cross-linkable hydrophilic block segment of the micelles formed in the aqueous solvent. Process.

  More specific examples of the method for producing the composition of the present invention include, but are not limited to, the following methods.

  The composition of the present invention can be prepared by mixing the block copolymer compound, the hydrophobic substance, the crosslinking agent, the solvent, the additive, and the like, which are the constituent components, and uniformly dissolving or dispersing. For example, a plurality of constituent components are mixed and crushed and dispersed by a dispersing machine such as a sand mill, ball mill, homogenizer, or nanomerzer to create an ink mother liquor, and a solvent or additive is added to adjust the physical properties. By carrying out like this, the hydrophobic block segment of a block copolymer compound can be adsorb | sucked to a hydrophobic substance, and a micelle can be formed. In order to prepare a uniform composition, an emulsification phase inversion method is 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 which has a self-crosslinkable functional group, without adding a crosslinking agent. Moreover, when using the polymer which has a crosslinkable functional group as a crosslinking agent, it is preferable to add before dispersion | distribution.

  Subsequently, this dispersion can be subjected to a crosslinking reaction with a crosslinkable functional group by heating under normal pressure or under pressure, irradiation with energy rays, reaction under specific conditions, or the like. At this time, the cross-linking reaction of the block copolymer compound occurs only in the micelle. That is, since the crosslinkable functional group is introduced into the hydrophilic block segment that does not become the outermost shell of the micelle, the cross-linking reaction is given priority in the micelle over the micelle.

  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 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, it is particularly preferable that the viscosity of the composition is low, the size of the fine particles in the composition is small, and the storage stability is excellent.

  In general, for example, the presence of coarse particles can be cited as one of the causes of discharge deterioration.

  The present invention can be said to be extremely useful in that it can provide a composition with few coarse particles, which is one of the causes of the deterioration of ejection, and a method for producing the same.

  Next, an image forming method, a liquid applying method and an image forming apparatus using the composition of the present invention will be described.

[Image Forming Method, Liquid Application Method, and Image Forming 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.

  The present invention includes a head (for example, an electrothermal converter or a laser beam) that generates thermal energy as energy used for ejecting ink jet ink, and ejects ink jet ink by the heat energy. Has an excellent effect. According to this method, high definition of drawing can be achieved. By using the ink-jet ink composition of the present invention, further excellent drawing can be performed.

  As a typical configuration and principle of the apparatus provided with the means for generating the heat energy, for example, the basic principle disclosed in US Pat. No. 4,723,129 and US Pat. No. 4,740,796 is used. Are preferably performed. This method can be applied to both a so-called on-demand type and a continuous type. In particular, in the case of the on-demand type, at least one that holds the liquid and gives a rapid temperature rise exceeding the nucleate boiling to the electrothermal transducer disposed corresponding to the flow path corresponding to the discharge information. By applying two drive signals, heat energy is generated in the electrothermal transducer. This is effective because film boiling occurs on the heat acting surface of the head, and as a result, bubbles in the liquid corresponding one-to-one with the drive signal can be formed. By the growth and contraction of the bubbles, the liquid is discharged through the discharge opening to form at least one droplet. It is more preferable that the drive signal has a pulse shape, because the bubble growth and contraction is performed immediately and appropriately, and thus it is possible to achieve liquid discharge particularly excellent in responsiveness. As this pulse-shaped drive signal, those described in US Pat. No. 4,463,359 and US Pat. No. 4,345,262 are suitable. In addition, if the conditions described in US Pat. No. 4,313,124 of the invention relating to the rate of temperature increase of the heat acting surface are adopted, further excellent discharge can be performed.

  As a configuration of the head, a combination configuration (straight liquid flow path or right-angle liquid flow path) of a discharge port, a liquid path, and an electrothermal transducer as disclosed in each of the above specifications is also included in the present invention. It is. In addition, a configuration using US Pat. No. 4,558,333 and US Pat. No. 4,459,600, which disclose a configuration in which the heat acting portion is arranged in a bent region, is also included in the present invention. In addition, the effect of the present invention is effective even in a configuration based on Japanese Patent Laid-Open No. 59-123670 that discloses a configuration in which a common slit is used as a discharge portion of the electrothermal transducer for a plurality of electrothermal transducers It is. The effect of the present invention is also effective as a configuration based on Japanese Patent Laid-Open No. 59-138461 which discloses a configuration in which an opening that absorbs a pressure wave of thermal energy corresponds to a discharge portion. In other words, regardless of the form of the head, according to the present invention, it is possible to reliably and efficiently discharge ink jet ink.

  Further, the present invention can be effectively applied to a full-line type head having a length corresponding to the maximum width of a recording medium in the image forming apparatus of the present invention. As such a head, either a configuration satisfying the length by a combination of a plurality of heads, or a configuration as one integrally formed head may be used.

  In addition, a serial type head that is fixed to the main body of the apparatus or mounted on the main body of the apparatus can be electrically connected to the main body of the apparatus and ink can be supplied from the main body. The present invention is also effective when a chip-type head is used.

  Furthermore, the apparatus of the present invention may further include a droplet removing unit. When such means is provided, a further excellent discharge effect can be realized.

  In addition, it is preferable to add preliminary auxiliary means or the like as the configuration of the apparatus of the present invention because the effects of the present invention can be further stabilized. Specifically, a capping unit for the head, a pressurizing or suction unit, a preheating unit for heating using an electrothermal converter or a heating element different from this, or a combination thereof, ink ejection A preliminary discharge means for performing discharge other than the above can be used.

  The most effective for the present invention is to execute the above-described film boiling method.

  In the apparatus of the present invention, the amount of ink ejected from each ejection port of the inkjet ink ejection head is preferably in the range of 0.1 picoliter to 100 picoliter.

  The ink composition of the present invention can also be used in an indirect recording apparatus using a recording method in which ink is printed on an intermediate transfer member and then transferred to a recording medium such as paper. Also, the present invention can be applied to an apparatus using an intermediate transfer member by a direct recording method.

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

(Synthesis Example 1)
<Synthesis of ABC type triblock copolymer 4>

  Polymerization was carried out as follows by known living cationic polymerization.

After the inside of the glass container fitted with the three-way cock was replaced with nitrogen, the adsorbed water was removed by heating to 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, monomer 1 (100 mmol) and IBEA (isobutyl vinyl ether ethyl acetate, 2.0 mmol) were dissolved in a toluene solution (300 mL) containing 0.10 M ethyl acetate. Then, ethylaluminum sesquichloride (1 mmol) was added at 0 ° C. to initiate the reaction of the A block segment. Monitoring was performed using gel permeation chromatography (GPC) to confirm the completion of polymerization of the A block segment. Next, monomer 2 (20 mmol) was added, and the reaction was monitored in the same manner as above to confirm the completion of polymerization of the B block segment. Finally, monomer 3 (20 mmol) was added, and the reaction was monitored in the same manner as above. At the end of the polymerization, 0.1 M ammonia methanol aqueous solution (30 mL) was added to the system to stop the reaction. After washing with 0.6M hydrochloric acid, the organic layer was removed under reduced pressure, and the residue was dissolved in THF (300 mL). Hydrazine (0.10 mol) was added, and the mixture was stirred at 60 ° C. for 3 hr, 0.1 M hydrochloric acid (50 mL) was added, and the mixture was further stirred for 30 min. The precipitate was precipitated in a 10% aqueous sodium carbonate solution, and the precipitated solid was washed with water. The solid content was dissolved in DMF (1 L), 12 M aqueous sodium hydroxide solution (15 mL) was added, and the mixture was stirred at 40 ° C. for 5 hr. After removing the solvent under reduced pressure, the residue was dissolved in water and purified by repeating methanol dialysis and water dialysis. After removing the solvent under reduced pressure and drying the residue under reduced pressure at 40 ° C., ABC type triblock copolymer 4 was obtained. Identification was performed from ¹ H-NMR spectrum and IR spectrum. The composition of each block was A: B: C = 50: 10: 10. From GPC (polystyrene equivalent, THF), the number average molecular weight was 12,000 and the molecular weight distribution was 1.15. The concentration of Na contained in the ICP was 100 ppm or less.

  In the polymer structural formula, “b” means a block bond.

(Synthesis Example 2)
<Synthesis of ABC type triblock copolymer 6>

  Polymerization was carried out in the same manner as in Synthesis Example 1.

After the inside of the glass container fitted with the three-way cock was replaced with nitrogen, the adsorbed water was removed by heating to 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, monomer 1 (100 mmol) and IBEA (isobutyl vinyl ether ethyl acetate, 2.0 mmol) were dissolved in a toluene solution (300 mL) containing 0.10 M ethyl acetate. Then, ethylaluminum sesquichloride (1 mmol) was added at 0 ° C. to initiate the reaction of the A block segment. Monitoring was performed using gel permeation chromatography (GPC) to confirm the completion of polymerization of the A block segment. Next, a mixed solution of monomer 2 (14 mmol) and monomer 5 (6 mmol) was added, and the reaction was monitored in the same manner as above to confirm the completion of polymerization of the B block segment. Finally, monomer 3 (20 mmol) was added, and the reaction was monitored in the same manner as above. At the end of the polymerization, 0.1 M ammonia methanol aqueous solution (30 mL) was added to the system to stop the reaction. After washing with 0.6M hydrochloric acid, the organic layer was removed under reduced pressure, and the residue was dissolved in THF (300 mL). Hydrazine (0.10 mol) was added, and the mixture was stirred at 60 ° C. for 3 hr, 0.1 M hydrochloric acid (50 mL) was added, and the mixture was further stirred for 30 min. The precipitate was precipitated in a 10% aqueous sodium carbonate solution, and the precipitated solid was washed with water. The solid content was dissolved in DMF (1 L), 12 M aqueous sodium hydroxide solution (15 mL) was added, and the mixture was stirred at 40 ° C. for 5 hr. After removing the solvent under reduced pressure, the residue was dissolved in water and purified by repeating methanol dialysis and water dialysis. After removing the solvent under reduced pressure and drying the residue under reduced pressure at 40 ° C., ABC type triblock copolymer 6 was obtained. Identification was performed from ¹ H-NMR spectrum and IR spectrum. The composition of each block was A: B: C = 50: 10: 10, and the copolymer composition in the B block segment was monomer 2: monomer 5 = 7: 3. From GPC (polystyrene equivalent, THF), the number average molecular weight was 10,000 and the molecular weight distribution was 1.12. The concentration of Na contained in the ICP was 100 ppm or less.

(Synthesis Example 3)
<Synthesis of ABC type triblock copolymer 8>

  Polymerization was carried out in the same manner as in Synthesis Example 1.

After the inside of the glass container fitted with the three-way cock was replaced with nitrogen, the adsorbed water was removed by heating to 250 ° C. in a nitrogen gas atmosphere. After returning the system to room temperature, monomer 1 (100 mmol) and IBEA (isobutyl vinyl ether ethyl acetate, 2.0 mmol) were dissolved in a toluene solution (300 mL) containing 0.10 M ethyl acetate. Then, ethylaluminum sesquichloride (1 mmol) was added at 0 ° C. to initiate the reaction of the A block segment. Monitoring was performed using gel permeation chromatography (GPC) to confirm the completion of polymerization of the A block segment. Next, monomer 7 (20 mmol) was added, and the reaction was monitored in the same manner as above to confirm the completion of polymerization of the B block segment. Finally, monomer 3 (20 mmol) was added, and the reaction was monitored in the same manner as above. At the end of the polymerization, 0.1 M ammonia methanol aqueous solution (30 mL) was added to the system to stop the reaction. After washing with 0.6 M hydrochloric acid, the organic layer was removed under reduced pressure, the residue was dissolved in DMF (1 L), 12 M aqueous sodium hydroxide solution (15 mL) was added, and the mixture was stirred at 40 ° C. for 5 hr. After removing the solvent under reduced pressure, the residue was dissolved in water and purified by repeating methanol dialysis and water dialysis. The solvent was removed under reduced pressure, and the residue was dried under reduced pressure at 40 ° C. to obtain ABC type triblock copolymer 8. Identification was performed from ¹ H-NMR spectrum and IR spectrum. The composition of each block was A: B: C = 50: 10: 10. From GPC (polystyrene equivalent, THF), the number average molecular weight was 11,000 and the molecular weight distribution was 1.24. The concentration of Na contained in the ICP was 100 ppm or less.

(Example 1)
The following components were co-dissolved in 200 parts by mass of THF and converted into an aqueous phase using 400 parts by mass of distilled water to obtain a composition.
-Block copolymer 4 obtained in Synthesis Example 1 10 parts by mass-Color material 10 parts by mass (carbon black, trade name: Monarch 880, manufactured by Cabot Corporation)
Block isocyanate 0.05 parts by mass (synthesized from butanol, MDI (4,4'-dicyanophenylmethane diisocyanate), polyethylene glycol (Mn2000) (molar ratio, 2: 2: 1)
Furthermore, after dispersing in an ultrasonic homogenizer over 10 minutes, a crosslinking reaction was performed at a temperature of 90 ° C. for 3 hours.

Subsequently, it refine | purified using the dialysis membrane (The product name: molecular porous membrane tube (MWCO: 3500) made by SPECTRU Laboratories), and obtained the composition. Water of this composition was distilled off to prepare a solid content concentration of 20% by mass to obtain an aqueous pigment dispersion. Using this dispersion, an ink composition 1 was prepared 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)
In the same manner as in Example 1, ink composition 2 using block copolymer 6 obtained in Synthesis Example 2 was prepared.

(Example 3)
In the same manner as in Example 1, ink composition 3 using block copolymer 8 obtained in Synthesis Example 3 was prepared.

Example 4
Instead of 10 parts by mass of Monarch 880 (trade name, manufactured by Cabot Corporation) which is carbon black as a coloring material, C.I. I. Ink composition 4 was prepared in the same manner as in Example 1 except that 10 parts by mass of Pigment Blue 15: 3 was used.

(Synthesis Example 4)
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, 1,400 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 dropping, the reaction was further continued at the same temperature for 15 hours to obtain a solution of the anionic group-containing organic polymer compound (A) having an acid value of 200 and a weight average molecular weight of 48,000.

(Synthesis Example 5)
940 parts of methyl ethyl ketone was charged into the reaction vessel of the automatic polymerization reactor used in Synthesis Example 4, 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 completion of the dropwise addition of the solution obtained by dissolving 60 parts of Methyl Pure Ketone) in 150 parts of methyl ethyl ketone, the reaction was continued at the same temperature for 15 hours to prepare a solution of the glycidyl group-containing organic polymer compound (B) having a weight average molecular weight of 21,000 Obtained.

(Preparation Example 1)
First, the polymer compound (A) obtained in Synthesis Example 4 and the polymer compound (B) obtained in Synthesis Example 5 are blended immediately before dispersion in an amount of A: B = 9: 1 in terms of solid content in terms of mass. To do. The molar equivalent of glycidyl group in 1000 g of the mixture before dispersion crosslinking was about 0.09.

  A mixing tank equipped with a cooling jacket was charged with the blended polymer compound mixture, 20% aqueous sodium hydroxide, water and carbon black (trade name: # 960, manufactured by Mitsubishi Chemical Corporation), and stirred and mixed. . Here, the charged amounts are 1,000 parts for carbon black and the amount of the blended polymer is 40% 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. .

  The mixed solution was passed through a dispersion apparatus (trade name: SC mill SC100 / 32 type, manufactured by Mitsui Mining Co., Ltd.) filled with zirconia beads having a diameter of 0.3 mm, and dispersed by a circulation method 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.

  After the dispersion, the dispersion stock solution was extracted from the mixing tank, and then the mixing tank and the dispersion device flow path were washed with 10,000 parts of water, and the diluted dispersion liquid was obtained together with the dispersion stock solution. The diluted dispersion was put into a glass distillation apparatus, and the whole amount of methyl ethyl ketone and a part of water were removed by atmospheric distillation.

  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 adjust the solid content concentration to 23% by mass. After coarse particles were removed from this dispersion by centrifugation, pure water was added to adjust the non-volatile content to obtain an aqueous black pigment dispersion having a solid content concentration of 20% by mass.

(Synthesis Example 6)
Polymerization was carried out as follows using a known group transfer polymerization. A 1 liter 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 molar THF solution of tetrabutylammonium m-chlorobenzoate as a catalyst was added. Initiator 1-methoxy-1-trimethylsiloxy-2-methylpropene 1.5 g (0.00862 mol) was injected. Then, 230 μl of a 1.0 molar THF solution of tetrabutylammonium m-chlorobenzoate was added over 130 minutes. Thereafter, 151.74 g (0.862 mol) of benzyl methacrylate (BZMA) was added as an A block over 60 minutes. 30 minutes after the polymerization progressed and 99% or more of the monomers had reacted, 221.07 g (0.862 mol) of ethoxytriethylene glycol methacrylate (ETEGMA) was added as a B block over a period of 60 minutes. One hour after the polymerization progressed and 99% or more of the monomers had reacted, 27.24 g (0.172 mol) of trimethylsilyl methacrylic acid (TMS-MAA) was added as a C block over 60 minutes. After polymerization progressed and 99% 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.

  This block copolymer was identified using NMR and GPC. Mn = 43800 and Mw / Mn = 1.18. The polymerization ratio was A: B: C = 100: 100: 20.

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

(Comparative Example 1)
Using the method of Example 1, ink composition 5 was prepared using the aqueous black pigment dispersion obtained in Preparation Example 1 so as to have the following composition.
-Aqueous pigment dispersion 25 parts by mass-Glycerol 8 parts by mass-Ethylene glycol 5 parts by mass-Ethanol 5 parts by mass-Emulgen 120 (trade name, manufactured by Kao Corporation) 0.05 parts by mass-Water 57 parts by mass (Comparative Example) 2)
10 parts by mass of the block copolymer obtained in Synthesis Example 6 and 10 parts by mass of Monarch 880 (trade name, manufactured by Cabot) as a coloring material are co-dissolved in 200 parts by mass of dimethylformamide, and 400 parts by mass of distilled water. The composition was obtained by converting into an aqueous phase. Furthermore, after dispersing in an ultrasonic homogenizer over 10 minutes, distilled water was added so that the solid content concentration was 1% by mass.

Next, a composition in which dimethylformamide was removed with a dialysis membrane (trade name: molecular porous membrane tube (MWCO: 3500) manufactured by SPECTRU Laboratories) was obtained. Water of this composition was distilled off to prepare a solid content concentration of 20% by mass to obtain an aqueous pigment dispersion. Using this dispersion, an ink composition 6 was prepared so as to have the following composition.
-Aqueous pigment dispersion 25 parts by mass-Glycerol 8 parts by mass-Ethylene glycol 5 parts by mass-Ethanol 5 parts by mass-Emulgen 120 (trade name, manufactured by Kao Corporation) 0.05 parts by mass-Water 57 parts by mass (Comparative Example) 3)
10 parts by mass of the block copolymer 8 obtained in Synthesis Example 3 and 10 parts by mass of Monarch 880 (trade name, manufactured by Cabot), which is carbon black as a coloring material, are co-dissolved in 200 parts by mass of THF, and 400 parts by mass of distilled water is used. To a water phase to obtain a composition. Furthermore, after dispersing in an ultrasonic homogenizer over 10 minutes, distilled water was added so that the solid content concentration was 1% by mass.

Subsequently, the composition which removed THF with the dialysis membrane (The product name: molecular porous membrane tube (MWCO: 3500) made by SPECTRU Laboratories) was obtained. Water of this composition was distilled off to prepare a solid content concentration of 20% by mass to obtain an aqueous pigment dispersion. Using this dispersion, an ink composition 7 was prepared so as to have the following composition.
-Aqueous pigment dispersion 25 parts by mass-Glycerol 8 parts by mass-Ethylene glycol 5 parts by mass-Ethanol 5 parts by mass-Emulgen 120 (trade name, manufactured by Kao Corporation) 0.05 parts by mass-Water 57 parts by mass [Evaluation]
The following evaluations were performed using the ink compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3.

(1) Filterability evaluation First, in order to confirm that the crosslinking reaction was not performed between micelles, the following filterability evaluation was performed. That is, 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. Therefore, it can be confirmed that when the filter is not discolored, at least coarse particles due to cross-linking 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 to 3 and Comparative Example 2, no filter discoloration was observed, and coarse particles could not be confirmed. On the other hand, discoloration was observed in the filter obtained by filtering the ink compositions of Comparative Examples 1 and 3. About the comparative example 3, since the polymer in which the crosslinking reaction is not performed is used, it is thought that the coarse particle was produced by aggregation.

(2) Stability evaluation with solvent Next, in order to confirm whether the crosslinking reaction has proceeded sufficiently and the dispersion resin is fixed, the following is performed for each ink composition before filtration. A solvent stability test was conducted. That is, each ink composition was added to 25 parts by mass of 250 parts by mass of THF and dispersed in an ultrasonic homogenizer for 10 minutes. Thereafter, THF was removed with a dialysis membrane (trade name: molecular porous membrane tube (MWCO: 3500) manufactured by SPECTRU Laboratories), water was distilled off, and the solid content concentration was adjusted to 20% by mass again. Using this aqueous dispersion, a solvent or the like 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 of Examples 1 to 3, precipitation was not observed, the crosslinking reaction was sufficiently advanced, and it was confirmed that the dispersion resin was fixed.

(3) Electron microscope observation Next, in order to confirm the micelle state, the filtrate after the filterability evaluation was stored for two months in an environment of 60 ° C., and then frozen and observed with an electron microscope using a cryo TEM. In the ink compositions of Examples 1 to 3, a substantially spherical structure was observed in almost the entire observation range.

  From this result, it is considered that the color material in the examples of the present application is completely encapsulated in the block copolymer, and a spherical polymer microsphere without intermicellar crosslinking is formed. On the other hand, in the ink composition of Comparative Example 2, a large number of irregular particles having an agglomerated particle size much larger than the substantially spherical structures found in Examples 1 to 6 were observed.

  As shown in Table 1, it was found that the ink compositions of the examples of the present invention were selectively subjected to a crosslinking reaction only in micelles, and an ink composition superior to the conventional one was obtained. .

(4) Printing evaluation The ink compositions prepared in Examples 1 to 3 were mounted on an inkjet printer BJF800 (trade name, manufactured by Canon Inc.). The entire surface of the glossy paper: Professional Photo Paper PR-101 (trade name, manufactured by Canon Inc.) was subjected to inkjet recording of a solid image. The printed solid images were all good images with no color unevenness and fading.

  Subsequently, the glossiness of each printed matter was measured by the following method. The measurement was performed using a product name “GP-200” manufactured by Murakami Color Research Laboratory Co., Ltd., 12V50W, incident beam stop φ1 mm, reflected beam stop φ1.5 mm, ND10 filter, incident angle 45 °, and tilt angle 0 °. The face plate was performed under the condition of 42.5. The average value of the maximum glossiness was determined for the evaluation color, and this was used as the average glossiness. As a result of the evaluation, the average glossiness value was 50 or more for any printed matter.

  Furthermore, when the printed matter obtained by printing the cyan ink composition of Example 4 was visually confirmed to have a bronzing phenomenon, it was confirmed to be a good image without the bronzing phenomenon.

  As described above, it was found that the printed matter by the ink composition in the example of the present invention showed an excellent effect.

  In the ink composition of the present invention, since the colorant is encapsulated by the crosslinked hydrophobic block segment in the dispersion polymer, the dispersibility is improved, and the dispersion stability and resolubility are excellent. It can be used for inkjet ink.

It is a schematic diagram which shows an example of the composition of this invention. It is a schematic diagram which shows an example of the micelle structure of FIG. It is a schematic diagram which shows an example of the micelle structure using the amphiphilic triblock copolymer as dispersion resin. It is a schematic diagram which shows the preferable crosslinked structure of the dispersion contained in the composition of this invention. It is a schematic diagram which shows an example of the block copolymer of this invention. It is a schematic diagram which shows the crosslinked state of the dispersion of a prior art.

Explanation of symbols

10 Dispersion 14 Hydrophobic substance (pigment)
15 Cross-linking part 20 Dispersing resin (amphiphilic block polymer compound)
30 Aqueous solvent

Claims (18)

At least a block copolymer compound having a hydrophilic block segment having a crosslinkable functional group and having both ends of a hydrophobic block segment and a non-crosslinkable hydrophilic block segment, a hydrophobic substance, and an aqueous solvent are prepared. A step of forming a micelle by adsorbing the block copolymer compound to the hydrophobic substance in the hydrophobic block segment in the aqueous solvent;
The inside of the micelle is cross-linked by cross-linking the cross-linkable functional group while suppressing cross-linking of the micelles by the steric hindrance action of the non-cross-linkable hydrophilic block segment of the micelle formed in the aqueous solvent. Process,
A method for producing a composition, comprising:   2. The hydrophilic block segment comprises an ionic hydrophilic block segment and a nonionic hydrophilic block segment, and at least one hydrophilic block segment is cross-linked. A method for producing the composition.   The method for producing a composition according to claim 1 or 2, wherein the crosslinkable functional group contains at least an amino group, a hydroxyl group, a carboxyl group, or a self-crosslinkable functional group.   4. The composition according to claim 3, wherein the crosslinkable functional group contains a self-crosslinkable functional group, and the self-crosslinkable functional group is a radically polymerizable unsaturated group or a hydrolyzable alkoxysilane group. Production method.   The method for producing a composition according to claim 1, 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 5, wherein the crosslinking agent is a hydrophilic or amphiphilic compound.   The method for producing a composition according to claim 6, wherein the crosslinking agent is a polymer compound.   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 8, wherein the colorant is a pigment.   The method for producing a composition according to any one of claims 1 to 9, wherein the hydrophilic block segment located at the end of the block copolymer compound is an ionic hydrophilic block segment.   The method for producing a composition according to any one of claims 1 to 9, wherein the hydrophilic block segment having a crosslinkable functional group in the block copolymer compound is a nonionic hydrophilic block segment.   The method for producing a composition according to any one of claims 1 to 11, wherein the main chain structure of each block segment of the block copolymer compound is a polyalkenyl ether structure.   The method for producing a composition according to claim 1, wherein the composition is an ink composition.   The method for producing a composition according to claim 13, wherein the ink composition is an inkjet composition.   A composition produced by the production method according to claim 1.   A composition produced by the production method according to claim 13 or 14.   An image forming method comprising a step of recording an image by applying the composition according to claim 16 to a medium.   An image forming apparatus comprising means for recording an image by applying the composition according to claim 16 to a medium.

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