JP2008050499A - Composition containing block polymer compound having different main chain backbone - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for satisfying both of dispersion stability and image characteristics, and further for forming a uniform film structure on media. <P>SOLUTION: This composition is provided by containing an amphiphilic block polymer compound equipped with a hydrophilic block segment having a main chain backbone (I) of a polyalkenyl ether and a hydrophobic block segment having a different main chain backbone (II) from the main chain backbone (I) and having more rigid structure of the main chain backbone (II) than that of the main chain (I), and an aqueous solvent. In the case that the amphiphilic block polymer forms a micelle structure including a hydrophobic substance in an aqueous solvent, a first polymer layer constituting the core part of the micelle structure becomes a more rigid layer as compared with a second polymer layer constituting the shell part of the micelle structure. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition containing an amphiphilic block polymer compound composed of block segments having different main chain skeletons and an aqueous solvent, for example, when a useful film forming agent or a coloring material is contained. The present invention relates to a composition useful as various inkjet inks.

  Polymer compounds as dispersion resins such as random polymers and block polymers are widely used as a dispersion for aqueous solvents, for example, as a coating agent and a surface modifier. As an aqueous dispersion material containing a hydrophobic substance, as a functional material, an agrochemical such as a herbicide or an insecticide, a medicine such as an anticancer agent, an antiallergic agent or an anti-inflammatory agent, and an ink having a colorant, Color materials such as toner are well known.

  Among these, when used in applications such as inks and toners having a coating agent or a colorant, the dispersion resin contains not only dispersion stability in an aqueous solvent but also physical properties of the film (adhesion). The improvement of the property, fastness, glossiness, etc. is also demanded.

For example, Patent Document 1 adopts a method of improving the fastness of an image by emulsion polymerization around a pigment and coating the pigment with a polymer.
JP 2003-306611 A

  However, in general, the more you think you want to improve film physical properties with a dispersion resin, the lower the dispersion stability in aqueous solvents and the properties of aqueous solutions (such as viscosity characteristics and ejection characteristics in inkjet inks). The trade-off relationship is generated. Therefore, in the configuration up to now including the above-mentioned patent documents, the performance of the two has been dealt with by balancing at a satisfactory level, and therefore, in particular, the physical properties of the film are not always satisfactory in practical use. In some cases, it was not possible.

  This trade-off relationship is believed to be due to the rigidity and mobility of the polymer. So, in part, there is a move to improve the trade-off situation by partially changing the polymer. However, only the micro functional separation in the polymer state is considered, and the macro functional separation in the dispersed state is hardly taken into consideration, so that it does not have a sufficient effect.

  From the above results, it has been practically difficult to achieve both image performance and dispersion performance, which are strongly demanded in the market, with a single polymer.

  The present invention has been made in view of the above circumstances, and provides a composition for achieving both dispersion stability and image characteristics, and further forming a uniform film structure on a medium.

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

  And it came to the conclusion that it is very effective to carry out functional separation by changing the main chain skeleton of the block polymer for the trade-off described above.

  That is, the first invention of the present invention is a composition comprising an amphiphilic block polymer compound having at least two or more block segments and an aqueous solvent, wherein the amphiphilic block polymer compound is polyalkenyl. A hydrophilic block segment having an ether main chain skeleton (I) and a hydrophobic block segment having a main chain skeleton (II) different from the main chain skeleton (I), the main chain skeleton (II) Is a composition that is more rigid than the main chain skeleton (I).

  According to a second aspect of the present invention, there is provided a composition containing an amphiphilic block polymer compound having at least two block segments and an aqueous solvent, wherein the amphiphilic block polymer compound is a polyalkenyl ether. A composition comprising a hydrophilic block segment having a main chain skeleton (I) and a hydrophobic block segment having a main chain skeleton having a Tg of 40 ° C. or more as a homopolymer.

  A third invention of the present invention comprises an amphiphilic block polymer compound having at least two or more block segments, a hydrophobic substance, and an aqueous solvent, wherein the amphiphilic block polymer compound is the aqueous solvent. In the composition forming a micelle structure including the hydrophobic substance therein, at least two main chain skeletons of the block segments of the amphiphilic block polymer compound are different, and the blocks having different main chain skeletons Each of the segments forms a first polymer layer that becomes the core portion of the micelle structure and a second polymer layer that becomes the shell portion of the micelle structure, and the first polymer layer becomes the second polymer layer. It is a composition characterized by being a rigid layer.

  Preferably, the hydrophilic block segment contains a repeating unit structure having an ionic functional group in a side chain. More preferably, the hydrophilic block segment is a composition further containing a repeating unit structure having a nonionic functional group in the side chain. Or the said hydrophilic block segment is a composition which further contains the block segment which has a repeating unit structure which has a nonionic functional group in a side chain.

  In the first and second inventions of the present invention, the composition may contain a hydrophobic substance.

  In the present invention, it is preferable to use a colorant, particularly a pigment, as the hydrophobic substance.

  In the present invention, amphiphilic block polymer compounds having different main chain skeletons are used. For example, a hydrophilic block segment having a main chain skeleton (I) of a polyalkenyl ether and a hydrophobic block having a main chain skeleton (II) which is different from the main chain skeleton (I) and is more rigid than the main chain skeleton (I) An amphiphilic block polymer compound having segments is used. This makes it possible to form a microsphere (micellar structure) with a rigid core part and a shell part that is flexible and has high mobility, and is excellent in dispersion stability in an aqueous solvent and coating on a medium. It is possible to provide a composition capable of exhibiting various film properties.

  In particular, when the present invention contains a coloring material in the composition, it is possible to achieve both excellent image characteristics and excellent dispersion stability, and further by forming a uniform film on the media. Compositions with image properties can be provided.

  Hereinafter, the present invention will be described in detail.

  In the present invention, an amphiphilic block polymer compound having a different main chain skeleton is used as the dispersion resin, the main chain skeleton of the hydrophobic block segment has a rigid structure, and the main chain skeleton of the hydrophilic block segment has a flexible and highly mobile structure. There is a feature in that. This amphiphilic block polymer forms a micelle structure enclosing the hydrophobic substance when a hydrophobic substance such as a pigment is present in the aqueous solvent.

  As shown in FIG. 1, in the present invention, a first polymer layer 3 composed of a rigid main chain skeleton of an amphiphilic block polymer compound 1 and a flexible main chain skeleton and a high mobility. A micelle structure 10 having two polymer layers 4 is formed. That is, the first polymer layer 3 is formed of a hydrophobic block segment included in the amphiphilic block polymer compound 1, and the second polymer layer 4 is a hydrophilic block segment included in the amphiphilic block polymer compound 1. Formed with.

  FIG. 2 is an enlarged schematic diagram of FIG. 1 and shows a state in which the hydrophobic substance 2 is packed (adsorbed) at the core portion by a rigid main chain skeleton that is the hydrophobic block segment 12. At this time, the hydrophilic block segment 11 having a soft main chain skeleton is coordinated in the shell portion. Therefore, the shell of the micelle structure 10 maintains a high polymer mobility, and forms a dense film by interlacing with other micelle structures at the time of film formation, and contributes to improving the adhesion to the media. can do.

  Here, the use of an amphiphilic block polymer compound with a different main chain skeleton as a dispersion resin is not limited to microscopic functional separation, but also to regional (core, shell) functional separation in a micelle structure. Because it can bring. If the functional separation is not performed to the area as in the case of the functional separation in the random polymer, the advantage is simply that it is easy to synthesize, and contributes to both the dispersion stability and the physical properties of the film in this application. It is thought not to.

  Further, by performing functional separation by changing the main chain skeleton of the block polymer, it is possible to favorably control the mobility of the block polymer. This is because when the block polymer forms a micelle structure, the main chain of the block polymer extends from the core in the shell direction, and therefore the main chain is dominant with respect to the mobility in the block polymer. . That is, it can also be said that the straight chain is oriented in the direction in which functional separation is desired.

  Therefore, according to the configuration of the present application, it is possible to obtain a great effect on the mobility by a slight design change of the polymer.

  The amphiphilic block polymer compound used in the present invention is characterized in that the main chain skeleton (I) of a polyalkenyl ether which can be generally a soft segment in an ink composition when a pigment is used as a hydrophobic substance is a hydrophilic block segment. And By doing so, dispersion stability in the solution and fusion between the micelle structures (particles) on the printed matter are helped, and a uniform film without graininess is formed, which can contribute to glossiness and fastness. Further, a rigid and hard main chain skeleton (II) different from the main chain skeleton (I) of the polyalkenyl ether is defined as a hydrophobic block segment. By doing so, the physical properties of the film can be strengthened, and high robustness can be realized. Furthermore, compared with a polymer hardened only by the side chain structure, it is expected that the adsorption property on the pigment surface layer is adsorbed in a packed state by the pigment surface layer and works more preferentially. In addition, the hydrophobic block segment can be shortened by contributing to hydrophobicity in the main chain portion.

  Specific application examples include near-infrared reflective materials, oxidation catalysts, deodorization / antibacterial, auxiliary heat, flue gas desalination, dioxin suppression, insect repellent effect, light scattering agent for liquid crystal panel backlight, fluorescent material, photoconductive Examples include materials and fillers. Furthermore, application to cosmetics such as UV protection and adsorption effects, pharmaceuticals, paints, toners, inks, printed materials or overcoat liquids for substrates, and the like can be mentioned. Since both high dispersion performance and image performance can be achieved, it can be suitably used as an ink or ink jet overcoat liquid. In addition, the usage method of the composition of this invention is not limited to the said application example.

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

  Amphiphilic means that both amphiphilic and lyophobic properties are present, and the amphiphilic block polymer compound is a polymer having at least one or more amphiphilic and lyophobic block segments. A compound. The above-mentioned amphiphilic property represents a property having a high affinity for the main solvent used, and the lyophobic property is a property having a low affinity for the solvent. In the present invention, since the main solvent is an aqueous solvent, the amphiphilic block polymer compound used in the present invention has at least one or more hydrophilic and hydrophobic block segments.

  The constitution of each block segment of the amphiphilic block polymer compound used in the present invention may consist of a repeating unit 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.

  Examples of the shape of the block structure of the amphiphilic block polymer compound used in the present invention include the following examples. Examples include a diblock polymer called AB, an ABA triblock polymer having the same block segment at both ends, and a triblock polymer called ABC having different block segments. In addition, the present invention includes those in which other polymer units are bonded to the triblock structure. For example, those having four different block segments called ABCD, those having the form ABCA, and block polymers having more block segments are also included in the present invention.

  In one embodiment of the present invention, characteristically, a hydrophilic block segment having a main chain skeleton (I) of a polyalkenyl ether and a hydrophobic block segment having a main chain skeleton (II) different from (I) An amphiphilic block polymer compound is used. However, the main chain skeleton (II) is more rigid than the main chain skeleton (I).

Examples of the rigid index described here include, but are not limited to, Tg, Young's modulus, Martens hardness, and the like. That is, the rigid main chain skeleton (II) is, for example, a main chain skeleton having Tg, a Young's modulus near the room temperature or a Martens hardness having a value larger than the value of the main chain skeleton (I) of the polyalkenyl ether. Point to. In other words, the mobility of the main chain skeleton (II) near room temperature is lower than that of the main chain skeleton (I), or the bond strength between the main chain skeletons (II) is stronger than that of the main chain skeleton (I). Point to. These indices may be compared, for example, between a hydrophobic block segment homopolymer and a hydrophilic block segment homopolymer. Tg can be determined by a differential scanning calorimeter (DSC) or dynamic viscoelasticity measurement, Young's modulus can be determined by a nanoindentation test or tensile test, and Martens hardness can be determined by a nanoindentation test. For example, in the Tg, it can be obtained by DSC822 using ^e (METTLER TOLEDO Edit trade name), measured at a Atsushi Nobori rate of 0.5 ° C. / min. By the way, if Tg is regarded as rigid, it is generally said that Tg and rigidity are strongly related, that is, if Tg is 40 ° C. or higher, which is sufficiently higher than room temperature, the polymer becomes glassy at room temperature. It can be said that it has sufficient hardness.

  In one embodiment of the amphiphilic block polymer compound used in the present invention, in an aqueous solvent, a core-shell type in which the hydrophilic block segment is the outer side (shell part) and the hydrophobic block segment is the inner side (core part). A micelle structure is formed. When a hydrophobic substance coexists in the composition, a dispersion containing the hydrophobic substance is formed. It is considered that the desired characteristics described in the present invention can be maximized by forming a microsphere having a rigid core portion and a shell portion having flexibility and high mobility. Stiffness here means that hardness and mobility are low. Specifically, it is as described above.

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

  The amphiphilic block polymer compound used in the present invention only needs to have a polyalkenyl ether main chain skeleton (I) as one of the hydrophilic block segments. Further, it is sufficient that one of the hydrophobic block segments has a main chain skeleton (II) that is different from the main chain skeleton (I) and is more rigid than the main chain skeleton (I). That is, it may have another main chain skeleton as one of other hydrophilic block segments or hydrophobic block segments.

  The main chain skeleton (I) of the polyalkenyl ether constituting the hydrophilic block segment preferably has a unit structure described in the following general formula (1).

In the above formula, A represents an alkenyl group. B represents a hydrogen atom or — (CH (X ₁ ) —CH (X ₂ ) —O) _p —X ₃ , — (CH ₂ ) _m — (O) _n —X _3, or at least one of these methylene groups is carbonyl. It represents a structure substituted with a group or an aromatic ring structure. p is an integer of 1 to 18, m is an integer of 1 to 36, and n is 0 or 1. X ₁ and X ₂ are each independently a hydrogen atom or —CH ₃ . X ₃ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, or COO—.

  Further, the amphiphilic block polymer compound used in the present invention may contain a repeating unit structure having an ionic functional group in the side chain as a hydrophilic block segment having a main chain skeleton (I) of polyalkenyl ether. preferable. Examples of the ionic functional group include organic acids. Preferred examples of organic acids include, but are not limited to, carboxylic acids, sulfonic acids, inorganic salts, and organic salts thereof.

  A repeating unit structure having a main chain skeleton (I) of polyalkenyl ether and having an ionic functional group in the side chain is exemplified by the following general formula (2).

(In the formula, A represents an optionally substituted alkenyl group. O represents an oxygen atom. D represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted.) The methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, and q represents an integer from 0 to 30, and when q is 2 or more, each D may be different. R represents —COOH, —COOR ² , —COO—M, —SO ₃ H, —SO ₃ R ² , —SO ₃ —M, where R ² is a straight chain having 1 to 5 carbon atoms or A branched alkyl group which may be substituted, or an aromatic ring which may be substituted is represented, and M represents a monovalent or polyvalent cation.)
Specific examples of the repeating unit represented by the general formula (2) include

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

  Furthermore, the amphiphilic block polymer compound used in the present invention may contain a repeating unit structure containing a nonionic functional group in the side chain as a hydrophilic block segment having a main chain skeleton (I) of polyalkenyl ether. Good. By having a nonionic functional group, even if environmental changes such as temperature and pH occur, the dispersion stability is not impaired, and an ink composition excellent in dischargeability particularly in the thermal ink jet method is obtained. The repeating unit structure having a nonionic functional group in the side chain may be contained as a random copolymer in the hydrophilic block segment having the main chain skeleton (I) of the polyalkenyl ether, or may be contained as a block segment. Good.

The repeating unit structure having the main chain skeleton (I) of polyalkenyl ether and having a nonionic functional group in the side chain is exemplified by the following general formula (3).
General formula (3):

(In the formula, A represents an optionally substituted alkenyl group. O represents an oxygen atom. D represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted.) The methylene group in the alkylene group may be substituted with an oxygen atom or an aromatic ring, and l represents an integer from 0 to 30, and when l is 2 or more, each D may be different. J is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms which may be substituted.)
Specific examples of the repeating unit represented by the general formula (3) include

However, it is not limited to these.

  Unlike the main chain skeleton (I), the main chain skeleton constituting the hydrophobic block segment may be more rigid than the main chain skeleton (I). Examples of such main chain skeletons include polystyrene skeleton, polyacrylic acid skeleton, polymethacrylic acid skeleton, polyacrylonitrile skeleton, polymethacrylonitrile skeleton, polyamide skeleton, polyimide skeleton, polyester skeleton, polyurethane skeleton, polycarbonate skeleton, poly Examples include, but are not limited to, an ether skeleton, a polyether sulfonic acid skeleton, and a polyvinyl chloride skeleton.

  Specific examples of such main chain skeleton (II) include

However, it is not limited to these. By the way, in Tg which is an index of rigidity ahead, Tg in the above structure is 40 ° C. or more.

  The amphiphilic block polymer compound used in the present invention may contain a soft hydrophobic block segment in the hydrophobic block segment, and the repeating unit structure forming the rigid main chain skeleton (II) and the soft hydrophobic repeating segment. It may be a copolymer with a unit structure. Examples of the copolymer include a binary or more random copolymer, a block copolymer, and a gradient copolymer.

  Furthermore, the hydrophobic block segment of the amphiphilic block polymer compound used in the present invention is more preferably one having a strong interaction with a hydrophobic substance, for example, an aromatic structure for a coloring material. More preferred are those having

  The aromatic described in the present invention refers to a cyclic unsaturated compound such as benzene, and refers to a conjugated unsaturated cyclic compound having a cyclic π electron cloud delocalized above and below the molecular plane. In addition, the aromatic described here may be an aromatic hydrocarbon composed only of a hydrocarbon, or a heteroaromatic compound containing an element other than carbon in the ring structure. Examples thereof include benzene, furan, pyridine, biphenyl, phenylpyridine, naphthalene, anthracene, and indene.

  The average polymerization degree ratio between the hydrophobic block segment and the hydrophilic block segment of the amphiphilic block polymer compound used in the present invention is preferably in the range of 5:95 to 95: 5, and 10:90 to 90:10. The range of is more preferable.

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

As a method for synthesizing the amphiphilic block polymer compound used in the present invention, first, polymerization of a hydrophilic block segment having a main chain skeleton (I) of a polyalkenyl ether will be described. Polymerization of the monomer that forms the main chain skeleton (I) of the polyalkenyl ether can be performed by cationic polymerization. Initiators include: protonic 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 _1.5 Examples include a combination of a Lewis acid such as AlCl _1.5 (R represents alkyl) and a cation source (the cation source is an adduct of proton acid, water, alcohol, vinyl ether and sulfonic acid, etc.). By allowing these initiators to coexist with the polymerizable compound (monomer), the polymerization reaction proceeds, and the hydrophilic block segment in the amphiphilic block polymer compound can be synthesized.

The polymerization method that is more preferably used in the present invention will be described. A number of methods for synthesizing polymers containing a polyvinyl ether structure have been reported (for example, JP-A-11-080221). Among them, the method by cation living polymerization by Aoshima et al. Is representative (Polymer Bulletin, Vol. 15, 417, 417, JP-A-11-322942, JP-A-11-322866). By conducting polymer synthesis using cationic living polymerization, homopolymers, copolymers composed of two or more monomers, and polymers such as block polymers, graft polymers, and gradient polymers can be accurately measured in length (molecular weight). Can be combined and synthesized. In addition, living polymerization can also be carried out in the HI / I ₂ system, HCl / SnCl ₄ system, or the like.

  Amphiphilic block polymer compounds having different main chain skeletons can be easily synthesized by a termination reaction between a cationic polymerization reaction solution and a polymer having a hydroxyl group at one end. Specifically, unlike the main chain skeleton (I) of polyalkenyl ether, the main chain skeleton (II) has a rigid main chain skeleton (II), and has a hydroxyl group at one end of the main chain. The hydrophobic polymer is added to the polyalkenyl ether cationic polymerization reaction solution. If it does so, reaction will stop because the cation active terminal of cationic polymerization forms a bond with the oxygen atom of a hydroxyl group, and the amphiphilic block polymer compound used for the present invention is compoundable.

  In addition, amphiphilic block polymer compounds having different main chain skeletons can be synthesized by a termination reaction by mixing a cationic polymerization reaction solution and an anion polymerization reaction solution. For example, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1990, 31 (1), 590. Specifically, unlike the polyalkenyl ether main chain skeleton (I), a main chain skeleton (II) which is more rigid than the main chain skeleton (I) is synthesized by anionic polymerization, and the anionic polymerization reaction liquid and the cation Mix with the polymerization reaction solution. By carrying out like this, the anion active terminal by anionic polymerization and the cation active terminal by cationic polymerization react, both bonds stop by forming a bond, and the amphiphilic block polymer compound used for this invention is compoundable.

  Further, the amphiphilic block polymer compound having a different main chain skeleton can be synthesized by adding a radical polymerizable monomer capable of cationic polymerization after the previous cationic polymerization reaction (Japanese Patent Laid-Open No. 2003-55420). . This method is a method in which radical polymerization is carried out from the end of a polymer obtained by cationic polymerization.

  The method for synthesizing the amphiphilic block polymer compound used in the present invention is not limited to the above example.

  In the composition of the present invention, the content of the amphiphilic block polymer compound is preferably in the range of 0.1% by mass to 90% by mass. More preferably, they are 1 mass% or more and 80 mass% or less.

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

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

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

  The hydrophobic substance used in the present invention is preferably a color material such as a pigment or a dye, and more preferably a pigment. The color material described in the present invention can be defined as an organic or inorganic colored compound, and preferably a compound insoluble in water or oily components. Specific examples include near-infrared reflective materials, oxidation catalysts, deodorization / antibacterial, auxiliary heat, flue gas desalination, dioxin suppression, insect repellent effect, light scattering agent for backlight of liquid crystal panel, fluorescent material, photoconductive material Etc. Furthermore, application examples such as application to cosmetics such as UV protection and adsorption effect, paints, toners, and inks can be given.

  Specific examples of inorganic color materials include cobalt blue, celsian blue, cobalt violet, cobalt green, zinc white, titanium white, light red, chrome oxide green, and mars black oxide pigments; viridan, yellow ocher, and alumina white. And hydroxide pigments such as ultramarine, talc and white carbon; metal powders such as gold powder, silver powder and bronze powder; and carbon black. Specific examples of the organic colorant include β-naphthol-based azo compounds, naphthol-AS-based azo compounds, monoazo-type or disazo-type acetoacetyl allylide-type azo compounds, pyrazone-type azo compounds, condensed azo pigments, and other azo-type compounds, Phthalocyanine compounds, subphthalocyanine compounds, porphyrin compounds, quinacridone compounds, isoindoline compounds, isoindolinone compounds, selenium compounds, perylene compounds, perinone compounds, thioindigo compounds, dioxazine compounds, quinophthalone compounds Compounds, diketopyrrolopyrrole compounds, or newly synthesized compounds. However, the color material used in the present invention is not limited to the above.

  Specific examples of the pigment when used as an ink composition are shown below.

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

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

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

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

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

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

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

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

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

  In addition, although the above demonstrated in the example in which a hydrophobic substance exists, this invention includes also about the form which does not have a hydrophobic substance in a micelle structure. In this case, it is effective for applications such as a coating agent and a gloss optimizer.

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

[Organic solvent]
Non-aqueous solvents such as hydrocarbon solvents, aromatic solvents, ether solvents, ketone solvents, ester solvents, amide solvents and the like can be mentioned.

[Aqueous solvent]
The composition of the present invention contains an aqueous solvent. Examples of the aqueous solvent include water and an aqueous solvent. As water, ion-exchanged water, pure water and ultrapure water from which metal ions and the like have been removed are preferable. Examples of the 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 present invention, the total content of the organic solvent and the aqueous solvent is preferably in the range of 20 to 95% by mass with respect to the total weight of the composition. More preferably, it is the range of 30-90 mass%.

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

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

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

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

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

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

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

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

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

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

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

(Synthesis Example 1)
Synthesis of polyphenyl methacrylate having a hydroxyl group at one end Mecerreys, G .; Moineau, Ph. Dubois, R.A. Jerome, J. et al. L. Hedrick, C.I. J. et al. Hawker, E .; E. Malmstrom and M.M. Trollsas: Angew. Chem. Int. Ed. , 37, 1274 (1998). That is, after the inside of the glass container equipped with the three-way battle 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, 1 mmol (mmol) of [NiBr ₂ (PPh ₃ ) ₃ ] was added. Further, a toluene solution of 70 mmol of phenyl methacrylate (PhMA) and 1 mmol of 2,2,2-tribromoethanol (CBr ₃ CH ₂ OH) was added, and N ₂ bubbling was performed for 15 minutes. The polymerization was started by heating to 75 ° C. The reaction was monitored using gel permeation chromatography (GPC) with time division of molecular weight. And it cooled at the stage where Mn is 9000, THF, 0.1M hydrochloric acid was added, and the target object was obtained by the reprecipitation fractionation by a heptane. When the compound was identified using NMR and GPC, it was Mn = 9000 and Mw / Mn = 1.20.

(Synthesis Example 2)
Synthesis of poly (4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi) -b-phenyl methacrylate (PhMA)) and hydrolysis thereof (Synthesis method: cationic polymerization reaction solution + one end Polymer compound having a hydroxyl group)
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, 20 mmol (mmol) of 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi) was added. Further, 160 mmol of ethyl acetate, 0.5 mmol of 1-isobutoxyethyl acetate, and 110 ml of toluene were added. Next, 2.0 mmol of ethylaluminum sesquichloride (an equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride) was added to initiate polymerization. The molecular weight was monitored using gel permeation chromatography (GPC) with time division. Then, when the Mn was 7000, a toluene solution of 5 mmol of polyphenyl methacrylate (Mn9000) synthesized in Synthesis Example 1 and having one hydroxyl group at one end was added to stop the polymerization reaction. The reaction mixture solution was diluted with dichloromethane and washed 3 times with 0.6M hydrochloric acid and then 3 times with distilled water. The obtained organic phase was concentrated and dried with an evaporator, and then vacuum-dried. Precipitation fractionation using THF and hexane and dialysis with a methanol solvent using a semipermeable membrane of cellulose were repeated. By doing so, the monomeric compound and unreacted polyphenyl methacrylate having a hydroxyl group at one end were removed to obtain the desired product. When the compound was identified using NMR and GPC, the average degree of polymerization ratio was VEEtPhCOOTBDMSi: PhMA = 30: 70, Mn = 15500, and Mw / Mn = 1.30.

  Further, the block polymer compound obtained here was dissolved in THF, 5 ml of 3N HCl / ethanol solution was added, and the mixture was stirred at room temperature (23 ° C.) for 3 hours, and then 20 ml of ethanol was added and further stirred for 3 hours. By doing so, hydrolysis of the (t-butyldimethylsilyl) ester in the VEEtPhCOOTBDMSi unit results in a carboxylic acid. This hydrolysis reaction was monitored by NMR. After the hydrolysis was completed 100%, the reaction was neutralized with sodium carbonate to complete the reaction. By removing excess salts by dialysis, an amphiphilic block polymer compound 1 in which the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton and the main chain of the hydrophobic block segment is a hard polymethacrylate skeleton is obtained. It was. The amphiphilic block polymer compound 1 was identified using NMR and IR.

(Synthesis Example 3)
Synthesis of poly (4-{(vinyloxy) ethoxy} benzoic acid ethyl ester (VEEtPhCOOEt) -b-styrene (St)) and hydrolysis thereof (Synthesis method: cationic polymerization reaction liquid + anionic polymerization reaction liquid)
In a high vacuum system at −78 ° C., 100 ml of 10 mM n-BuLi / THF was added and stirred. Then, 0.1 mol of styrene was heated and evaporated, and added to the cooled solvent to polymerize styrene. In the same manner as in Synthesis Example 2, instead of 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi), 4-{(vinyloxy) ethoxy} benzoic acid ethyl ester (VEEEtPhCOOEt) was used. Polymerized. When the completion of polymerization of VEEtPhCOOEt was confirmed by monitoring of GPC (Mn = 7300, Mw / Mn = 1.20), both reactions were stopped by mixing the polymerization reaction liquid of styrene and the polymerization reaction liquid of VEEtPhCOOEt. did. Purification was performed in the same manner as in Synthesis Example 2 to obtain the target product. When the compound was identified using NMR and GPC, the average polymerization degree ratio was VEEtPhCOOEt: St = 30: 90, Mn = 16000, and Mw / Mn = 1.20.

  Furthermore, the block polymer compound obtained here was hydrolyzed in a mixed solution of dimethylformamide and sodium hydroxide to hydrolyze the ethyl ester portion of the VEEtPhCOOEt unit, thereby obtaining a sodium salified block polymer. By removing excess NaOH by dialysis, an amphiphilic block polymer compound 2 in which the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton and the main chain of the hydrophobic block segment is a hard polystyrene skeleton is obtained. It was. The amphiphilic block polymer compound 2 was identified using NMR and IR.

(Synthesis Example 4)
Synthesis of ethyl poly (6- (2-vinyloxy) ethoxycaproate (VEEtPenCOOEt) -b-styrene (St)) and hydrolysis thereof (Synthesis method: radical polymerization after cationic polymerization)
In the same manner as in Synthesis Example 2, 15 mmol of ethyl 6- (2-vinyloxy) ethoxycaproate (VEEtPenCOOEt), styrene monomer (50 mmol), and 0.5 mmol of a hydrogen chloride adduct of isobutyl vinyl ether were mixed and polymerized. That is, 15 mmol of ethyl 6- (2-vinyloxy) ethoxycaproate (VEEtPenCOOEt), 50 mmol of styrene monomer, 22 mmol of phenyl bromide, and 25 ml of toluene were added to a glass container equipped with a dry three-way cock. After cooling to −78 ° C., a toluene solution containing 0.5 mmol of a hydrogen chloride adduct of isobutyl vinyl ether and a toluene solution containing 0.25 mmol of tin tetrachloride were added to initiate polymerization. Monitoring was performed by GPC, and when Mn was 6000, degassed methanol was added to stop the reaction. Here, 20 ml of a toluene solution containing 0.15 mmol of pentamethylcyclopentadienylbistriphenylphosphine monochloridorthenium (II) complex and 1.5 mmol of dibutylamine was added. And it heated to 100 degreeC and the superposition | polymerization of styrene was started. When the polymerization of styrene was completed by monitoring with GPC, the reaction solution was cooled in a dry ice-methanol bath at −78 ° C. to terminate the polymerization. The obtained reaction mixture was treated with an adsorbent (trade name: KYOWARD, manufactured by Kyowa Chemical Co., Ltd.) and purified in the same manner as in Synthesis Example 1 to obtain the desired product. When the compound was identified using NMR and GPC, the average polymerization degree ratio was VEEtPenCOOEt: St = 30: 90, Mn = 14000, and Mw / Mn = 1.25.

  Amphiphilic block polymer compound in which hydrolysis reaction is performed in the same manner as in Synthesis Example 3, the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton, and the main chain of the hydrophobic block segment is a hard polystyrene skeleton 3 was obtained.

(Synthesis Example 5)
Synthesis of poly (4-{(vinyloxy) ethoxy} benzoic acid ethyl ester (VEEEtPhCOOEt) -b-methoxyethoxyethyl vinyl ether (MOEOVE) -b-styrene (St)) and hydrolysis thereof (synthesis method: cationic polymerization reaction solution + Anionic polymerization reaction solution)
Styrene was synthesized in the same manner as in Synthesis Example 3. Further, 15 mmol of 4-{(vinyloxy) ethoxy} benzoic acid ethyl ester (VEEEtPhCOOEt) was polymerized by the same method as in Synthesis Example 3. When the completion of polymerization of VEEtPhCOOEt was confirmed by monitoring GPC (Mn = 6000, Mw / Mn = 1.18), 10 mmol of methoxyethoxyethyl vinyl ether (MOEOVE) was added, and the polymerization was continued. After confirming completion of MOEOVE polymerization by GPC monitoring (Mn = 8500 at this stage, Mw / Mn = 1.26), the reaction was mixed with the previous styrene polymerization reaction solution to stop both reactions. Purification was performed in the same manner as in Synthesis Example 2 to obtain the target product. The compound was identified using NMR and GPC. The average polymerization degree ratio was VEEtPhCOOEt: MOEOVE: St = 30: 20: 90, and Mn = 19000 and Mw / Mn = 1.30.

  Amphiphilic block polymer compound in which hydrolysis reaction is performed in the same manner as in Synthesis Example 3, the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton, and the main chain of the hydrophobic block segment is a hard polystyrene skeleton 4 was obtained.

(Synthesis Example 6)
Synthesis of poly ([4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi) -r-methoxyethoxyethyl vinyl ether (MOEOVE)]-b-phenyl methacrylate (PhMA)) and hydrolysis thereof (Synthesis method: cationic polymerization reaction liquid + polymer compound having a hydroxyl group at one end)
In the same manner as in Synthesis Example 2, 4-{(vinyloxy) ethoxy} benzoic acid (t-butyldimethylsilyl) ester (VEEEtPhCOOTBDMSi) 15 mmol and methoxyethoxyethyl vinyl ether (MOEOVE) 10 mmol were mixed and polymerized. The completion of polymerization of VEEtPhCOOTBDMSi and MOEOVE was confirmed by monitoring GPC (Mn = 10000, Mw / Mn = 1.19). At this stage, a toluene solution of 5 mmol of polyphenyl methacrylate (Mn 9000) synthesized in Synthesis Example 1 and having a hydroxyl group at one end was added to stop the polymerization reaction. Purification was performed in the same manner as in Synthesis Example 2 to obtain the target product. When the compound was identified using NMR and GPC, the average degree of polymerization ratio was VEEtPhCOOTBDMSi: MOEOVE: PhMA = 30: 20: 90, Mn = 18500, and Mw / Mn = 1.32.

  Amphiphilic block polymer compound in which hydrolysis reaction is performed in the same manner as in Synthesis Example 3, the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton, and the main chain of the hydrophobic block segment is a hard polystyrene skeleton 5 was obtained.

(Synthesis Example 7)
Synthesis of poly (tbutyl-4-vinylbenzoate (StCOOTB) -b-styrene (St)) and its hydrolysis Into a high vacuum system at -78 ° C, 100 ml of 10 mM n-BuLi / THF was added and stirred. Next, 0.1 mol of styrene was vaporized at a temperature and added to the cooled solvent to polymerize styrene. After the polymerization of styrene, 0.03 mol of tbutyl-4-vinylbenzoate diluted with 80 ml of THF was added through a breakable seal provided in the system. After completion of the polymerization of t-butyl-4-vinylbenzoate, quenching methanol was added by a breakable seal method to stop the reaction.

  The reaction mixture solution was reprecipitated into a methanol solvent, and the precipitate was collected using a glass filter. The precipitate was vacuum-dried and confirmed to be the target diblock polymer by NMR and analysis using GPC. The average polymerization degree ratio was StCOOTB: St = 30: 90, Mn = 15000, and Mw / Mn = 1.33.

  Furthermore, the block polymer obtained here is hydrolyzed using hydrobromic acid, and the amphiphile in which the main chain of the hydrophilic block segment is a hard polystyrene skeleton and the main chain of the hydrophobic block segment is a hard polystyrene skeleton. Block polymer compound 6 was obtained.

(Synthesis Example 8)
Synthesis of poly (6- (2-vinyloxy) ethoxycaproate ethyl (VEEtPenCOOEt) -b-isobutyl vinyl ether (IBVE)) and hydrolysis thereof In the same manner as in Synthesis Example 4, 6- (2-vinyloxy) ethoxycaproic acid Ethyl (VEEtPenCOOEt) was polymerized. When the completion of polymerization of VEEtPenCOOEt was confirmed by monitoring GPC (Mn = 6500, Mw / Mn = 1.20), 20 mmol of isobutyl vinyl ether (IBVE) was added and polymerization was continued. After confirming the completion of the polymerization of IBVE by monitoring of GPC (Mn = 9500 at this stage, Mw / Mn = 1.25), 0.3% by mass of ammonia / methanol aqueous solution was added to terminate the polymerization. Purification was performed in the same manner as in Synthesis Example 2 to obtain a bowl-shaped compound.

  Amphiphilic block in which hydrolysis reaction is carried out in the same manner as in Synthesis Example 3, the main chain of the hydrophilic block segment is a soft polyalkenyl ether skeleton, and the main chain of the hydrophobic block segment is a soft polyalkenyl ether skeleton Polymer compound 7 was obtained.

(Example 1)
6 parts by mass of the amphiphilic block polymer compound 1 of Synthesis Example 2 was dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes, and then 94 parts by mass of distilled water was added to convert to an aqueous phase. Thereafter, the pH was adjusted to 9 using an aqueous sodium hydroxide solution. Then, tetrahydrofuran was removed by distillation under reduced pressure. Subsequently, 32 parts by mass of glycerin, 20 parts by mass of ethylene glycol, 20 parts by mass of ethanol, 0.2 part by mass of Emulgen 120 (trade name, manufactured by Kao Corporation) and 228 parts by mass of water were added to obtain a polymer composition 1. .

(Example 2)
A polymer composition 2 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 2 of Synthesis Example 3 was used.

(Example 3)
A polymer composition 3 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 3 of Synthesis Example 4 was used.

Example 4
A polymer composition 4 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 4 of Synthesis Example 5 was used.

(Example 5)
A polymer composition 5 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 5 of Synthesis Example 6 was used.

(Comparative Example 1)
A polymer composition 6 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 6 of Synthesis Example 7 was used.

(Comparative Example 2)
A polymer composition 7 was obtained in the same manner as in Example 1 except that the amphiphilic block polymer compound 7 of Synthesis Example 8 was used.

(Example 6)
After 6 parts by mass of the amphiphilic block polymer compound 1 of Synthesis Example 2 and 4 parts by mass of M880 (trade name, manufactured by Cabot) as a coloring material were dispersed in tetrahydrofuran with an ultrasonic homogenizer for 10 minutes, distillation was performed. 90 parts by mass of water was added to convert to an aqueous phase. Thereafter, the pH was adjusted to 9 using an aqueous sodium hydroxide solution. Then, tetrahydrofuran was removed by distillation under reduced pressure. Subsequently, 32 parts by mass of glycerin, 20 parts by mass of ethylene glycol, 20 parts by mass of ethanol, 0.2 part by mass of Emulgen 120 (trade name, manufactured by Kao Corporation) and 228 parts by mass of water were added to obtain ink composition 1. .

(Example 7)
An ink composition 2 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 2 of Synthesis Example 3 was used.

(Example 8)
An ink composition 3 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 3 of Synthesis Example 4 was used.

Example 9
An ink composition 4 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 4 of Synthesis Example 5 was used.

(Example 10)
An ink composition 5 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 5 of Synthesis Example 6 was used.

(Comparative Example 3)
An ink composition 6 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 6 of Synthesis Example 7 was used.

(Comparative Example 4)
An ink composition 7 was obtained in the same manner as in Example 6 except that the amphiphilic block polymer compound 7 of Synthesis Example 8 was used.

(Evaluation)
Using the polymer compositions 1 to 7 obtained in Examples 1 to 5 and Comparative Examples 1 to 2, the ink compositions 1 to 7 obtained in Examples 6 to 10 and Comparative Examples 3 to 4, the following was performed. Was evaluated.

(1) Dispersion stability test As a factor indicating the dispersion stability of a polymer compound in an aqueous solvent, the solubility or dispersibility of the polymer compound in water is the most important. The turbidity when dispersed and dissolved can be verified. That is, a polymer aqueous solution of a polymer compound having high dispersion stability has high transparency, and a polymer aqueous solution of a polymer compound having low dispersion stability causes white turbidity or precipitation.

  In this application, as a result of visually observing the states of the polymer compositions 1 to 7 obtained in Examples 1 to 5 and Comparative Examples 1 and 2, the compositions in Examples 1 to 5 and Comparative Example 2 were highly transparent. Although there was no cloudiness, it was a cloudy composition in Comparative Example 1.

(2) Print image rubbing test The rubbing mode of the coated paper printed image of the pigment-dispersed ink includes the sharpness of the print image caused by rubbing with a nail etc. The deformation of the printed dots caused by rubbing with a nail or the like, which is noticeable in the color density region, can be mentioned. These two rubbing modes can greatly degrade the image quality and must be satisfied under any rubbing conditions. In these two modes, the strength of the polymer film formed by printing with the polymer compound, the molecular weight of the polymer compound, the hydrophilic-hydrophobic balance, the adsorptivity of the polymer compound to the pigment, etc. are important factors. Conceivable.

  In the present application, the ink compositions 1 to 7 obtained in Examples 6 to 10 and Comparative Examples 3 to 4 were subjected to a rubbing test for the above two modes. That is, these ink compositions are filled in a print head of an ink jet printer (trade name: BJF 930, manufactured by Canon Inc.) and printed on a coated paper of PR101 (brand name manufactured by Canon Inc.) with a solid print and a print density with respect to the solid print. Printing was performed so as to be approximately 20%. Then, after drying for two days, a scratch test with a nail was performed. The deformation of the dots was confirmed with an optical microscope. As a result, although the ink compositions 1 to 5 obtained in Examples 6 to 10 gave good results in any mode, the ink compositions 6 to 7 obtained in Comparative Examples 3 to 4 were at least Good results were not obtained in any of the scratch tests.

  As described above, in the present invention, the soft hydrophilic block segment having a polyalkenyl ether main chain skeleton (I) and the hydrophobic block segment having a rigid main chain skeleton (II) different from (I) The contained amphiphilic block polymer compound is used. By doing so, it will be understood that it is possible to provide a composition that can achieve both a high level of dispersion stability in an aqueous solvent and good scratch resistance on a recording medium, which have been in a trade-off relationship. .

  Furthermore, the glossiness and film property in the present invention were evaluated by the following methods.

(3) Evaluation of Glossiness Evaluation (2) The glossiness of solid print images by the ink compositions 1 to 5 and 6 obtained in the scratch test of the print image was visually compared. Compared with the image of the ink composition 6 obtained in Comparative Example 3, the images of the ink compositions 1 to 5 obtained in Examples 6 to 10 were good with a significant difference in glossiness.

(4) Evaluation of film properties Polymer compositions 1 to 5 and 6 were cast on a glass substrate, and after drying for two days, the surface shape of the cast film was observed with AFM.

  The granular feeling observed in the polymer composition 6 obtained in Comparative Example 1 is not observed in the polymer compositions 1 to 5 obtained in Examples 1 to 5, and has no granular feeling and high smoothness. A film was formed.

  These are presumed that since the hydrophilic block segment part constituting the shell part of the micelle structure formed in the present invention has high mobility, the micelle structures are compatible with each other and a polymer film without graininess is formed. Is done. This smoothness is considered to be one of the reasons why the printed image of the present invention is excellent in evaluation (3) gloss evaluation.

  As described above, in the present invention, by forming a sphere having a rigid core portion and a shell portion having flexibility and high mobility, the dispersion stability in an aqueous solvent and the formation on a medium are achieved. It is possible to provide a composition that can be made favorable as film properties.

  In particular, when the present invention contains a coloring material in the composition, it is possible to achieve both excellent image characteristics and excellent dispersion stability, and further to form a uniform film on the media, thereby further improving the image. A composition of the property can be provided.

It is a schematic diagram showing the micelle structure formed in the composition of this invention. FIG. 2 is an enlarged schematic diagram of FIG. 1 showing a state in which a hydrophobic block segment having a rigid main chain is adsorbed to a hydrophobic substance.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Amphiphilic block polymer compound 2 Hydrophobic substance 3 1st polymer layer 4 2nd polymer layer 10 Micellar structure 11 Hydrophilic block segment 12 Hydrophobic block segment

Claims (11)

In a composition comprising an amphiphilic block polymer compound having at least two or more block segments, and an aqueous solvent,
The amphiphilic block polymer compound comprises a hydrophilic block segment having a main chain skeleton (I) of polyalkenyl ether, and a hydrophobic block segment having a main chain skeleton (II) different from the main chain skeleton (I); And the main chain skeleton (II) has a more rigid structure than the main chain skeleton (I). In a composition comprising an amphiphilic block polymer compound having at least two or more block segments, and an aqueous solvent,
The amphiphilic block polymer compound comprises a hydrophilic block segment having a main chain skeleton (I) of polyalkenyl ether and a hydrophobic block segment having a main chain skeleton having a Tg of 40 ° C. or more as a homopolymer. A composition characterized by comprising: An amphiphilic block polymer compound having at least two block segments, a hydrophobic substance, and an aqueous solvent are contained, and the amphiphilic block polymer compound encapsulates the hydrophobic substance in the aqueous solvent. In the composition forming the micelle structure,
The first polymer layer and the micelle which are different in at least two main chain skeletons among the block segments of the amphiphilic block polymer compound, and each of the block segments having different main chain skeletons serves as a core part of the micelle structure. A composition characterized in that a second polymer layer to be a shell part of a structure is formed, and the first polymer layer is a rigid layer as compared with the second polymer layer.   The composition according to claim 1 or 2, wherein the hydrophilic block segment contains a repeating unit structure having an ionic functional group in a side chain.   The composition according to claim 4, wherein the hydrophilic block segment further contains a repeating unit structure having a nonionic functional group in a side chain.   The composition according to claim 4, wherein the hydrophilic block segment further contains a block segment having a repeating unit structure having a nonionic functional group in a side chain.   The composition according to any one of claims 1, 2, and 4 to 6, further comprising a hydrophobic substance.   The composition according to claim 7, wherein the hydrophobic substance is a coloring material.   The composition according to claim 8, wherein the colorant is a pigment.   The composition according to claim 3, wherein the hydrophobic substance is a coloring material.   The composition according to claim 10, wherein the colorant is a pigment.

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