JP2008050503A - Composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition that achieves both dispersion stability and image properties and further forms a uniform film structure on a medium. <P>SOLUTION: The composition comprises at least an amphiphilic block polymer compound having a hydrophobic block segment containing a unit structure represented by general formula (1) or (2) (wherein R<SB>1</SB>to R<SB>9</SB>and R<SB>11</SB>to R<SB>19</SB>are each independently a hydrogen atom or a 1-4C linear or branched organic group) and a hydrophilic block segment, and an aqueous solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition containing a novel block polymer of a specific structure.

As a method of dispersing a hydrophobic substance in an aqueous solvent, there are a self-dispersion type in which a hydrophobic substance is surface-treated and a resin dispersion type in which an amphiphilic resin is attached around a water-insoluble material. Among these, the dispersion resin used for the resin dispersion type has been studied as a dispersion for aqueous solvents in many fields, particularly as an ink composition (Patent Documents 1 to 3). In recent years, reports have been made to improve the light resistance and gas resistance of an image on a print medium using this dispersion resin. However, to date, no satisfactory results have been obtained for both image performance and dispersion performance. The reason for this is that the polymer structure needs to be rigid in order to improve the above-mentioned image characteristics, while the polymer having a rigid structure has a high hydrophobicity due to the structure, resulting in a decrease in dispersion stability. It is done. That is, it is considered that in order to achieve both image performance and dispersion performance, it is indispensable to satisfy both trade-offs between the rigidity of the polymer structure and the dispersion stability.
JP 2004-352819 A Japanese Patent Application Laid-Open No. 2005-281691 JP 2005-532470 A

  In order to solve this phenomenon, we used a known polymer compound that is commercially available as a dispersion material, and investigated the compatibility between image performance and dispersion performance. However, it was difficult for the polymer compound we used for the study to achieve both a high level of dispersion performance and image characteristics on the media.

  In addition, it is conceivable to achieve both dispersion performance and image characteristics with polymer alloys and additives, but this compatibility can be realized with a single polymer compound due to the demand for uniformity of printed images and dispersions. That is desired in the market. However, as described above, it has been practically difficult to achieve both image performance and dispersion performance, both of which are currently strongly demanded in the market, using 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.

  The present invention contains at least an amphiphilic block polymer compound having a hydrophobic block segment and a hydrophilic block segment containing the unit structure described in the following general formula (1) or (2), and an aqueous solvent. It is a composition characterized by these.

In the above formula, R _{1 to} R ₉ and R _{11 to} R ₁₉ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

  The glass transition temperature of a homopolymer consisting only of the hydrophilic block segment is preferably 70 ° C. or lower. The hydrophilic block segment may have, for example, a polyalkenyl ether main chain skeleton.

  In the above composition, the amphiphilic block polymer compound preferably forms a micelle structure in which the core portion is the hydrophobic block segment and the shell portion is the hydrophilic block segment in the aqueous solvent. In the composition further containing a hydrophobic substance, the hydrophobic substance is preferably included in the micelle structure.

  As described above, according to the present invention, there is provided a composition that exhibits both excellent image characteristics and excellent dispersion stability, and further exhibits excellent image characteristics by forming a uniform film on a medium. can do.

  Hereinafter, the present invention will be described in detail.

  The composition of the present invention comprises at least an amphiphilic block polymer compound having a hydrophobic block segment and a hydrophilic block segment containing a unit structure described in the following general formula (1) or (2), and an aqueous solvent. contains.

In the above formula, R _{1 to} R ₉ and R _{11 to} R ₁₉ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

  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 can be formed. And, it becomes a sphere having a rigid core portion formed by the hydrophobic block segment and a shell portion having a flexible and high mobility formed by the hydrophilic block segment, so that the desired characteristics described in the present invention are obtained. It is thought that it is obtained to the maximum.

  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 a plurality of different types of block segment structures are linked on a polymer chain, and refers to what is also called 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 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.

The hydrophobic block segment included in the both amphiphilic block polymer compounds used in the present invention contains the unit structure described in the general formula (1) or (2). The hydrophobic block segment containing the unit structure described in the general formula (1) can be formed by polymerizing the corresponding β-pinene or a derivative thereof. For example, a hydrophobic block segment containing a unit structure described in the general formula (1) in which R _{1 to} R ₃ and R _{6 to} R ₉ are hydrogen atoms and R ₄ and R ₅ are methyl groups has β -It can be formed by polymerizing pinene.

  The polymerization method of β-pinene or a derivative thereof can be performed by, for example, a cationic polymerization method. Since it is possible to synthesize a block polymer simply by adding monomers sequentially, it is preferable to carry out the living cationic polymerization method. Polymerization of β-pinene is described, for example, in European Polymer Journal, 40, p398 (2004), Polymer Preprints, Japan Vol. 50, no. 1, p516 (2006).

  The hydrophobic block segment containing the unit structure described in the general formula (2) may be formed by hydrogenation after forming the hydrophobic block segment containing the unit structure described in the general formula (1). it can. For example, a reaction formula for hydrogenating a hydrophobic block segment formed by polymerizing β-pinene is shown below. Hydrogenation is described, for example, in Polymer Preprints, Japan Vol. 50, no. 1, p516 (2006).

  The hydrophilic block segment included in the amphiphilic block polymer compound used in the present invention is not particularly limited as long as it is hydrophilic. As the main chain skeleton of the hydrophilic block segment, for example, polyalkenyl ether skeleton, polystyrene skeleton, polyacrylic acid skeleton, polymethacrylic acid skeleton, polyacrylonitrile skeleton, polymethacrylonitrile skeleton, polyamide skeleton, polyimide skeleton, polyester skeleton, Examples include, but are not limited to, a polyurethane skeleton, a polycarbonate skeleton, a polyether skeleton, a polyether sulfonic acid skeleton, and a polyvinyl chloride skeleton. Since it becomes a soft main chain skeleton, it is preferable to form a main chain skeleton of polyalkenyl ether.

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

In the above formula, A represents a polyalkenyl 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—.

  The glass transition temperature of the homopolymer consisting only of this hydrophilic block segment is preferably 70 ° C. or lower.

  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, a method for forming a main chain skeleton of a polyalkenyl ether serving as a hydrophilic block segment will be described. The polymerization of the monomer that forms the main chain skeleton 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 causing these initiators to coexist with a polymerizable compound (monomer), the polymerization reaction proceeds, and a hydrophilic block segment in the 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.

  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 showed in the example where a hydrophobic substance exists, this invention also includes the form which does not have a hydrophobic substance in a micelle. 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. Note that “-b-” is a symbol indicating a block polymer, and “-r-” is a symbol indicating a random polymer. Moreover, the identification of the compound in each step was performed using NMR and GPC.

(Synthesis Example 1)
<Synthesis of diblock polymer poly [BPN-b-AA]>
A block: β-pinene (BPN)
B block: Acrylic acid (AA)
A diblock polymer poly [BPN-b-EA] was synthesized according to a method for synthesizing a block polymer of β-pinene and styrene described in European Polymer Journal, 40, p398 (2004) (EA: ethyl acrylate).

That is, first, 4.0 mL of a toluene solution of β-pinene (BPN) and 2-chloropropionic acid ethyl ester was prepared at −78 ° C. in a nitrogen atmosphere. To the solution, 1.0 mL of a toluene mixed solution of titanium tetrachloride (TiCl ₄ ), isopropoxytitanium chloride (TiCl ₃ (OiPr)), and tetrabutylammonium chloride (nBu ₄ NCl) was added to initiate polymerization. The molecular weight was monitored in a time-resolved manner using molecular sieve column chromatography (GPC) and NMR, and when the average number of repeating units of β-pinene reached 100, the reaction was quenched by adding methanol. Thereafter, it was washed 3 times with hydrochloric acid and then 3 times with distilled water. Furthermore, reprecipitation which throws an organic phase into methanol was performed several times, and then the polymer was purified by vacuum drying to obtain poly [BPN] ₁₀₀ -EA-Cl.

Next, 0.1 g of poly [BPN] ₁₀₀ -EA-Cl obtained in the above step was mixed with ethyl acrylate (EA), copper chloride (CuCl), bipyridine (bpy) (molar ratio 1/1 / in a toluene solution). 3) Mixed with 2.0 mL. Then, EA was polymerized at 100 ° C. in a dry argon atmosphere. The resulting reaction solution was centrifuged to remove the copper-containing residue, and the supernatant was vacuum dried to remove unreacted EA. Furthermore, reprecipitation put into methanol was performed several times, and then the polymer was purified by vacuum drying to obtain diblock polymer poly [BPN-b-EA]. The obtained poly [BPN-b-EA] had Mn = 12,500, Mw / Mn = 1.39, and the average polymerization degree ratio was A: B = 100: 30. In addition, Mn is a number average molecular weight and Mw is a weight average molecular weight.

  The diblock polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and aqueous sodium hydroxide to hydrolyze the ethyl ester portion of the EA unit in the B block, and the diblock polymer that was sodium chlorided was Obtained. Further, diblock polymer poly [BPN-b-AA], in which sodium chloride-acrylic acid (AA) unit is converted into free carboxylic acid unit by neutralizing with 0.1N hydrochloric acid in aqueous dispersion, Obtained.

  Moreover, it was 70 degrees C or less when the glass transition temperature of the homopolymer which consists of an applicable hydrophilic segment was measured with the differential scanning calorimeter (trade name: EXSTAR6000, Seiko Instruments Inc.).

(Synthesis Example 2)
<Synthesis of diblock polymer poly [BPN-b-VEEtPhCOOH]>
A block: β-pinene (BPN)
B block: 4- (2-vinyloxy) ethoxybenzoic acid (VEEtPhCOOH)
Polymer Preprints, Japan Vol. 50, no. The diblock polymer poly [BPN-b-VEEtPhCOOH] was synthesized according to the cationic polymerization method of β-pinene described in 1, p516 (2006).

  That is, in a nitrogen atmosphere, 5.0 mmol (mmol) of BPN, 0.6 mmol of ethyl acetate, 0.05 mmol of 1-isobutoxyethyl acetate, and 20 ml of toluene were added, and the reaction system was cooled. When the system temperature reached 0 ° C., 1.0 mmol of ethylaluminum sesquichloride (an equimolar mixture of diethylaluminum chloride and ethylaluminum dichloride) was added to initiate polymerization. The molecular weight was monitored in a time-sharing manner using molecular sieve column chromatography (GPC) to confirm the completion of polymerization of the A block.

  Next, as a B block component, a toluene solution of 2.5 mmol ethyl 4- (2-vinyloxy) ethoxybenzoate VEEtPhCOOEt was added to continue the polymerization. The polymerization reaction was stopped by adding a 0.3% by mass ammonia / methanol aqueous solution to the system. The reaction mixture solution was diluted with dichloromethane and washed 3 times with 0.6 mol / L hydrochloric acid and then 3 times with distilled water. The obtained organic phase was concentrated, dried and vacuum dried with an evaporator, and repeatedly dialyzed in a methanol solvent using a semipermeable membrane of cellulose to remove the monomeric compound, and the diblock polymer poly [BPN -B-VEEtPhCOOEt] was obtained. The obtained poly [BPN-b-VEEtPhCOOEt] had Mn = 14000 and Mw / Mn = 1.40, and the average degree of polymerization was A: B = 100: 20.

  The diblock polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and aqueous sodium hydroxide to hydrolyze the ethyl ester part of the VEEtPhCOOEt unit in the B block, and the diblock polymer converted into sodium chloride was Obtained. Further, the diblock polymer poly [BPN- in which the 4- (2-vinyloxy) ethoxybenzoic acid unit, which was neutralized with 0.1 N hydrochloric acid in an aqueous dispersion, became a free carboxylic acid unit. b-VEEtPhCOOH] was obtained.

  Moreover, it was 70 degrees C or less when the glass transition temperature of the homopolymer which consists of an applicable hydrophilic segment was measured with the differential scanning calorimeter (trade name: EXSTAR6000, Seiko Instruments Inc.).

(Synthesis Example 3)
<Synthesis of Diblock Polymer Poly [BPN-b- (MOEOVE-r-VEEtPhCOOH)]>
A block: β-pinene (BPN)
B block: Diethylene glycol methyl vinyl ether and 4- (2-vinyloxy) ethoxybenzoic acid (MOEOVE-r-VEEEtPhCOOH)
Along with 2.5 mmol (mmol) of ethyl 4- (2-vinyloxy) ethoxybenzoate VEEtPhCOOEt, which is a monomer of the B block component in Synthesis Example 2, 1.0 mmol of diethylene glycol methyl vinyl ether (MOEOVE) was added. Except for this, a diblock polymer poly [BPN-b- (MOEOVE-r-VEEEtPhCOOEt)] was synthesized under the same synthesis conditions as in Synthesis Example 2. The obtained poly [BPN-b- (MOEOVE-r-VEEEtPhCOOEt)] had Mn = 16200 and Mw / Mn = 1.39, and the average degree of polymerization was A: B = 100: 35. Further, the average polymerization degree ratio of MOEOVE and VEEtPhCOOEt in the B block was 20:15.

  The diblock polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and aqueous sodium hydroxide to hydrolyze the ethyl ester part of the VEEtPhCOOEt unit in the B block, and the diblock polymer converted into sodium chloride was Obtained. Further, the diblock polymer poly [BPN-, which was neutralized with 0.1 N hydrochloric acid in an aqueous dispersion and the sodium salified 4- (2-vinyloxy) ethoxybenzoic acid unit became a free carboxylic acid unit. b- (MOEOVE-r-VEEtPhCOOH)] was obtained.

  Moreover, it was 70 degrees C or less when the glass transition temperature of the homopolymer which consists of an applicable hydrophilic segment was measured with the differential scanning calorimeter (trade name: EXSTAR6000, Seiko Instruments Inc.).

(Synthesis Example 4)
<Synthesis of Triblock Polymer / Poly [BPN-b-MOEOVE-b-VEEEtPhCOOH]>
A block: β-pinene (BPN)
B block: Diethylene glycol methyl vinyl ether (MOEOVE)
C block: 4- (2-vinyloxy) ethoxybenzoic acid (VEEtPhCOOH)
Instead of 2.5 mmol (mmol) of ethyl 4- (2-vinyloxy) ethoxybenzoate VEEtPhCOOEt, which is the monomer of the B block component in Synthesis Example 2, 1.0 mmol of diethylene glycol methyl vinyl ether (MOEOVE) was added. Except for this, A block and B block were polymerized in the same manner as in Synthesis Example 2. After completion of polymerization of the B block was confirmed by monitoring using GPC and NMR, 5.0 mmol of ethyl 4- (2-vinyloxy) ethoxybenzoate was added as a C block component, and polymerization was continued. The others were synthesized under the same synthesis conditions as in Synthesis Example 2 to synthesize triblock polymer poly [BPN-b-MOEOVE-b-VEEEtPhCOOEt]. The obtained poly [BPN-b-MOEOVE-b-VEEEtPhCOOEt] had Mn = 16000 and Mw / Mn = 1.38, and the average degree of polymerization was A: B: C = 100: 20: 15. .

  By hydrolyzing the obtained triblock polymer in a mixed solution of dimethylformamide and aqueous sodium hydroxide, the ethyl ester portion of the VEEtPhCOOEt unit in the C block is hydrolyzed, and the sodium salt triblock polymer is converted into a salt. Obtained. Further, the triblock polymer poly [BPN- in which the 4- (2-vinyloxy) ethoxybenzoic acid unit, which has been neutralized with 0.1N hydrochloric acid in an aqueous dispersion, is converted into a free carboxylic acid unit. b-MOEOVE-b-VEEtPhCOOH] was obtained.

  Moreover, it was 70 degrees C or less when the glass transition temperature of the homopolymer which consists of an applicable hydrophilic segment was measured with the differential scanning calorimeter (trade name: EXSTAR6000, Seiko Instruments Inc.).

(Synthesis Example 5)
<Synthesis of diblock polymer poly [HBPN-b-AA]>
A block: β-pinene hydrogen adduct (HBPN)
B block: Acrylic acid (AA)
Polymer Preprints, Japan Vol. 50, no. 1, p516 (2006) and synthesized according to the β-pinene hydrogenation method. Specifically, hydrogenation is performed on the unsaturated carbon bond existing in the BPN of the diblock polymer poly [BPN-b-EA] obtained in Synthesis Example 1 to thereby produce the diblock polymer poly [ HBPN-b-EA] was synthesized.

That is, after the diblock polymer poly [BPN-b-EA] obtained in Synthesis Example 1 was dissolved in o-xylene, p-toluenesulfonyl hydrazide was added and reacted at 135 ° C. under a hydrogen pressure of 10 kg / cm ² . It was. And the diblock polymer poly [HBPN-b-EA] which added hydrogen to the double bond of the BPN unit was obtained. Confirmation of hydrogen addition to the double bond was performed using NMR. The obtained poly [HBPN-b-EA] had Mn = 12,500, Mw / Mn = 1.39, and the average polymerization degree ratio was A: B = 100: 30.

  The diblock polymer obtained here was hydrolyzed in a mixed solution of dimethylformamide and aqueous sodium hydroxide to hydrolyze the ethyl ester portion of the EA unit in the B block, and the diblock polymer that was sodium chlorided was Obtained. Further, diblock polymer poly [HBPN-b-AA], in which sodium chloride-treated acrylic acid (AA) unit is converted into free carboxylic acid unit by neutralization with 0.1N hydrochloric acid in aqueous dispersion. Obtained.

  Moreover, it was 70 degrees C or less when the glass transition temperature of the homopolymer which consists of an applicable hydrophilic segment was measured with the differential scanning calorimeter (trade name: EXSTAR6000, Seiko Instruments Inc.).

(Example 1)
5 parts by mass of the diblock polymer poly [BPN-b-AA] synthesized in Synthesis Example 1 was dissolved in 100 parts by mass of tetrahydrofuran and converted into an aqueous phase using 400 parts by mass of distilled water. 0.1 mL of 0.1N sodium hydroxide aqueous solution was added thereto, and after further dispersing for 10 minutes with an ultrasonic homogenizer, tetrahydrofuran was removed by distillation under reduced pressure to obtain a polymer dispersion composition.

Using a dynamic light scattering device (trade name: DLS-7000, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter d and the dispersion index μ / G ² of the dispersed particles of the polymer dispersion composition obtained by the above method are used. It was measured. In order not to change the pH, the measurement was performed by diluting 100 times with an aqueous sodium hydroxide solution having the same concentration. As a result, the average particle size was 52 nm, the dispersity index μ / G ² was 0.12, and it was confirmed that the diblock polymer poly [BPN-b-AA] was uniformly dispersed in water.

(Example 2)
A polymer dispersion composition was obtained in the same manner as in Example 1 except that the diblock polymer poly [BPN-b-VEEtPhCOOH] synthesized in Synthesis Example 2 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained polymer dispersion composition were measured by the same method as in Example 1. As a result, the average particle size was 55 nm, the dispersity index μ / G ² was 0.10, and it was confirmed that the diblock polymer poly [BPN-b-VEEtPhCOOH] was uniformly dispersed in water.

(Example 3)
A polymer dispersion composition was obtained in the same manner as in Example 1 except that the diblock polymer poly [BPN-b- (MOEOVE-r-VEEEtPhCOOH)] synthesized in Synthesis Example 3 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained polymer dispersion composition were measured by the same method as in Example 1. As a result, the average particle size was 65 nm, the dispersion index μ / G ² was 0.10, and the diblock polymer poly [BPN-b- (MOEOVE-r-VEEEtPhCOOH)] was uniformly dispersed in water. It was confirmed.

Example 4
A polymer dispersion composition was obtained in the same manner as in Example 1 except that the triblock polymer poly [BPN-b-MOEOVE-b-VEEtPhCOOH] synthesized in Synthesis Example 4 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained polymer dispersion composition were measured by the same method as in Example 1. As a result, the average particle diameter was 61 nm, the dispersity index μ / G ² was 0.10, and the triblock polymer poly [BPN-b-MOEOVE-b-VEEEtPhCOOH] was uniformly dispersed in water. confirmed.

(Example 5)
A polymer dispersion composition was obtained in the same manner as in Example 1 except that the diblock polymer poly [HBPN-b-AA] synthesized in Synthesis Example 5 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained polymer dispersion composition were measured by the same method as in Example 1. As a result, the average particle size was 58 nm, the dispersity index μ / G ² was 0.11, and it was confirmed that the diblock polymer poly [HBPN-b-AA] was uniformly dispersed in water.

(Example 6)
5 parts by mass of carbon black (trade name: M880, manufactured by Cabot) and 5 parts by mass of the diblock polymer poly [BPN-b-AA] synthesized in Synthesis Example 1 were dissolved in 100 parts by mass of tetrahydrofuran, and distilled water was added. It converted into the water phase using 400 mass parts. 0.1 mL of 0.1N sodium hydroxide aqueous solution was added thereto, and after further dispersing for 10 minutes with an ultrasonic homogenizer, tetrahydrofuran was removed by vacuum distillation to obtain a carbon black dispersion composition.

The average particle diameter d and the dispersion index μ / G ² of the dispersed particles of the carbon black dispersion composition obtained by the above method were measured in the same manner as in Example 1. As a result, the average particle size was 89 nm, the dispersity index μ / G ² was 0.17, and it was confirmed that the diblock polymer poly [BPN-b-AA] was uniformly dispersed in water.

  Furthermore, regarding the obtained carbon black dispersion composition, it was confirmed using EF-TEM observation by cryotransfer that carbon black was present in the core portion where the block polymer was formed.

(Example 7)
A carbon black dispersion composition was obtained in the same manner as in Example 6 except that the diblock polymer poly [BPN-b-VEEtPhCOOH] synthesized in Synthesis Example 2 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained carbon black dispersion composition were measured in the same manner as in Example 1. As a result, the average particle size was 93 nm, the dispersity index μ / G ² was 0.15, and it was confirmed that the diblock polymer poly [BPN-b-VEEtPhCOOH] was uniformly dispersed in water.

  Furthermore, regarding the obtained carbon black dispersion composition, it was confirmed using EF-TEM observation by cryotransfer that carbon black was present in the core portion where the block polymer was formed.

(Example 8)
A carbon black dispersion composition was obtained in the same manner as in Example 6 except that the diblock polymer poly [BPN-b- (MOEOVE-r-VEEEtPhCOOH)] synthesized in Synthesis Example 3 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained carbon black dispersion composition were measured in the same manner as in Example 1. As a result, the average particle diameter was 95 nm, the dispersion index μ / G ² was 0.15, and the diblock polymer poly [BPN-b- (MOEOVE-r-VEEEtPhCOOH)] was uniformly dispersed in water. It was confirmed.

  Furthermore, regarding the obtained carbon black dispersion composition, it was confirmed using EF-TEM observation by cryotransfer that carbon black was present in the core portion where the block polymer was formed.

Example 9
A carbon black dispersion composition was obtained in the same manner as in Example 6 except that the triblock polymer poly [BPN-b-MOEOVE-b-VEEEtPhCOOH] synthesized in Synthesis Example 4 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained carbon black dispersion composition were measured in the same manner as in Example 1. As a result, the average particle size is 95 nm, the dispersion index μ / G ² is 0.15, and the triblock polymer poly [BPN-b-MOEOVE-b-VEEEtPhCOOH] is uniformly dispersed in water. confirmed.

  Furthermore, regarding the obtained carbon black dispersion composition, it was confirmed using EF-TEM observation by cryotransfer that carbon black was present in the core portion where the block polymer was formed.

(Example 10)
A carbon black dispersion composition was obtained in the same manner as in Example 6 except that the diblock polymer poly [HBPN-b-AA] synthesized in Synthesis Example 5 was used.

Further, the average particle diameter d and the dispersity index μ / G ² of the dispersed particles of the obtained carbon black dispersion composition were measured in the same manner as in Example 1. As a result, the average particle diameter was 82 nm, the dispersity index μ / G ² was 0.16, and it was confirmed that the diblock polymer poly [HBPN-b-AA] was uniformly dispersed in water.

  Furthermore, regarding the obtained carbon black dispersion composition, it was confirmed using EF-TEM observation by cryotransfer that carbon black was present in the core portion where the block polymer was formed.

(Filterability evaluation)
It was confirmed using the following filterability evaluation that the carbon black-containing dispersion was stably dispersed without agglomeration in water. That is, 20 mL of each carbon black dispersion composition obtained in Example 6 to Example 10 was taken and pressure filtered using a membrane filter (trade name: AP20 manufactured by Millipore). As a result, it was confirmed that any carbon black dispersion composition could be filtered without clogging and stably dispersed.

(Polymer film hardness evaluation)
It was confirmed by the following method that the obtained block polymer had sufficient hardness. That is, 5 mL of each polymer dispersion composition obtained in Example 1 to Example 5 was taken, dropped onto a glass substrate, and then heated to 130 ° C. to obtain a polymer film. When the polymer film on the glass substrate was gradually cooled to room temperature and then rubbed with a nail, no scratch was observed on any polymer film, and it was confirmed that the film was sufficiently hard.

Furthermore, regarding the polymer films of the block polymers obtained in Synthesis Example 1 and Synthesis Example 2, Martens hardness was measured using an indentation test (trade name: Fisherscope H-100, manufactured by Fisher Instruments Co., Ltd.). As a result, the Martens hardness was 150 N / mm ² or more with respect to any of the block polymer compounds in Synthesis Example 1 and Synthesis Example 2, which was a sufficient hardness.

  From the above, it was confirmed that the block polymers in the examples of the present invention have sufficient hardness and can be stably dispersed in an aqueous solvent.

(Evaluation of uniformity of polymer film)
The uniformity of the polymer film obtained by the above polymer film hardness evaluation was confirmed using the following method. That is, the polymer films of the block polymers obtained in Synthesis Example 1 and Synthesis Example 3 were measured using an atomic force microscope (trade name: SPA-500, manufactured by Seiko Instruments Inc.). As a result, the block polymer film of Synthesis Example 1 was slightly grainy. On the other hand, in the block polymer film of Synthesis Example 3, a substantially uniform polymer film without graininess was observed.

  As described above, the composition of the present invention is stably dispersed without being clogged, and the film produced by the composition described in the present invention has high strength and further forms a uniform film on the media. Therefore, both excellent image characteristics and dispersibility can be achieved.

Claims (5)

It contains at least an amphiphilic block polymer compound having a hydrophobic block segment and a hydrophilic block segment containing the unit structure described in the following general formula (1) or (2), and an aqueous solvent. Composition.

In the above formula, R _{1 to} R ₉ and R _{11 to} R ₁₉ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.   The composition according to claim 1, wherein a glass transition temperature of the homopolymer consisting only of the hydrophilic block segment is 70 ° C or lower.   The composition according to claim 1 or 2, wherein the hydrophilic block segment has a main chain skeleton of polyalkenyl ether.   The amphiphilic block polymer compound has a micelle structure in which the core portion is the hydrophobic block segment and the shell portion is the hydrophilic block segment in the aqueous solvent. 4. The composition according to any one of 3.   5. The composition according to claim 4, further comprising a hydrophobic substance, wherein the hydrophobic substance is encapsulated in the micelle structure.