Aqueous dispersion, aqueous ink, recording medium and method for producing aqueous dispersion

Abstract

SOLUTION: To provide an aqueous dispersion including: a vinyl chloride polymer; an aqueous dispersion polymer; and solid particles, where weight average molecular weight of the aqueous dispersion polymer is 5000 or more and 50000 or smaller, a median diameter by dynamic light scattering of the solid particles is less than 1 μm, the solid particles have on their surfaces, hydrophilic functional groups, the aqueous dispersion includes 10 pts.mass or more and less than 70 pts.mass of a vinyl chloride polymer with respect to 100 pts.mass of a total amount of the vinyl chloride polymer, aqueous dispersion polymer, and solid particles, the aqueous dispersion includes 5 pts.mass or more and 40 pts.mass or less of an aqueous dispersion polymer with respect to 100 pts.mass of a total amount of the vinyl chloride polymer, aqueous dispersion polymer, and solid particles, the aqueous dispersion includes 5 pts.mass or more and less than 50 pts.mass of the solid particles with respect to 100 pts.mass of the total amount of the vinyl chloride polymer, aqueous dispersion polymer, and solid particles.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an aqueous dispersion, an aqueous ink, a recording medium, and a method for producing the aqueous dispersion. [Background technology]

[0002] Patent documents 1 to 3 disclose synthetic resin emulsions containing a copolymer of vinyl chloride monomer and other polymerizable monomer as a main component. Patent documents 4 to 5 disclose vinyl chloride resin emulsions obtained by polymerizing vinyl chloride monomer in the presence of a specific type of oligomer. Patent document 6 discloses a coating composition containing silica fine particles, a surfactant, and a resin emulsion. Patent document 7 discloses an aqueous dispersion obtained by emulsion polymerization of ethylenically unsaturated monomers (particularly carboxyl group-containing monomers) using an aqueous resin composition and water-dispersed inorganic particles as emulsion stabilizers. Patent document 8 discloses a glossy paper for inkjet recording for oil-based pigment inks having a cast coat layer obtained by mixing a vinyl chloride resin and spherical colloidal silica. Patent document 9 discloses polyvinyl chloride resin particles obtained by polymerizing vinyl chloride monomer in the presence of colloidal silica. (Prior art document) (Patent Documents) (Patent Document 1) Japanese Patent Application Laid-open No. 112990 / 1983 (Patent Document 2) Japanese Patent Application Laid-Open No. 51-74081 (Patent Document 3) Japanese Patent Application Laid-open No. 15471 / 1983 (Patent Document 4) International Publication No. 2010 / 140647 (Patent Document 5) International Publication No. 2020 / 166660 (Patent Document 6) JP 2012-241181 A (Patent Document 7) JP 2008-239779 A (Patent Document 8) JP 2020-026042 A (Patent Document 9) JP 2017-095587 A Summary of the Invention [Means for solving the problem]

[0003] In a first aspect of the present invention, an aqueous dispersion is provided. The aqueous dispersion includes, for example, a vinyl chloride polymer. The aqueous dispersion includes, for example, a water-dispersed polymer. The aqueous dispersion includes, for example, solid particles. The weight average molecular weight of the water-dispersed polymer is, for example, 5,000 or more and 50,000 or less. The median diameter of the solid particles measured by a dynamic light scattering method is, for example, less than 1 μm. The solid particles have, for example, hydrophilic functional groups on their surfaces. The aqueous dispersion includes, for example, a vinyl chloride polymer in an amount of 10 parts by mass or more and less than 70 parts by mass relative to a total of 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles. The aqueous dispersion includes, for example, a water-dispersed polymer in an amount of 5 parts by mass or more and 40 parts by mass or less relative to a total of 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles. The aqueous dispersion includes, for example, a solid particle in an amount of 5 parts by mass or more and less than 50 parts by mass relative to a total of 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles.

[0004] In any of the above aqueous dispersions, the aqueous dispersion polymer may have at least one of a carboxy group and a urethane group. In any of the above aqueous dispersions, the aqueous dispersion polymer may include at least one of a polymer of an ethylenically unsaturated group-containing monomer and a urethane-based polymer. In any of the above aqueous dispersions, the aqueous dispersion polymer may include at least one of an acrylic acid ester oligomer, a styrene-acrylic acid ester oligomer, and a polycarbonate-based urethane oligomer.

[0005] In any of the above aqueous dispersions, the vinyl chloride polymer and the aqueous dispersion polymer may form a core-shell structure in which the aqueous dispersion polymer covers the vinyl chloride polymer. In any of the above aqueous dispersions, the solid particles may be bonded to the aqueous dispersion polymer forming the core-shell structure by intermolecular interactions.

[0006] In any of the above aqueous dispersions, (i) the content of the surfactant having a molecular weight of 1,000 or less in the aqueous dispersion is 100 g / m 3 In any of the above aqueous dispersions, (ii) the ratio of the mass of the surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride polymer may be less than 0.001% by mass.

[0007] In any of the above aqueous dispersions, the ratio of the mass of the solid content of the aqueous dispersion to the mass of the aqueous dispersion may be 10 mass % or more and 50 mass % or less.

[0008] In any of the above aqueous dispersions, the solid particles may contain colloidal silica having a median diameter of 6 nm or more and 100 nm or less, as measured by dynamic light scattering.

[0009] In the second aspect of the present invention, an aqueous dispersion is provided. The aqueous dispersion is obtained, for example, by polymerizing vinyl chloride monomer in a reaction liquid. The reaction liquid is obtained, for example, by mixing vinyl chloride monomer, water-dispersed polymer, solid particles, and an aqueous solvent. The weight average molecular weight of the water-dispersed polymer is, for example, 5,000 or more and 50,000 or less. The median diameter of the solid particles is, for example, less than 1 μm as measured by a dynamic light scattering method. The solid particles have, for example, hydrophilic functional groups on their surfaces. In the aqueous dispersion, the reaction liquid contains, for example, 10 parts by mass or more and less than 70 parts by mass of vinyl chloride monomer relative to 100 parts by mass of the total of vinyl chloride monomer, water-dispersed polymer, and solid particles. In the aqueous dispersion, the reaction liquid contains, for example, 5 parts by mass or more and 40 parts by mass or less of water-dispersed polymer relative to 100 parts by mass of the total of vinyl chloride monomer, water-dispersed polymer, and solid particles. In the above aqueous dispersion, the reaction liquid contains, for example, 5 parts by mass or more and less than 50 parts by mass of solid particles per 100 parts by mass in total of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles.

[0010] In any of the above aqueous dispersions, (i) the concentration of the surfactant having a molecular weight of 1,000 or less in the aqueous dispersion is 100 g / m 3In any of the above aqueous dispersions, (ii) the ratio of the mass of the surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride monomer may be less than 0.001% by mass.

[0011] In a third aspect of the present invention, there is provided an aqueous ink comprising, for example, any of the aqueous dispersions according to the first aspect or any of the aqueous dispersions according to the second aspect.

[0012] In a fourth aspect of the present invention, a recording medium is provided, which includes, for example, a composition derived from any of the aqueous dispersions according to the first aspect, or a composition derived from any of the aqueous dispersions according to the second aspect.

[0013] In a fifth aspect of the present invention, a recording medium is provided. The recording medium includes, for example, a substrate. The recording medium includes, for example, a recording layer disposed on at least one side of the substrate. In the recording medium, the recording layer includes, for example, a vinyl chloride polymer. In the recording medium, the recording layer includes, for example, a water-dispersed polymer. In the recording medium, the recording layer includes, for example, solid particles. The weight average molecular weight of the water-dispersed polymer is, for example, 5,000 or more and 50,000 or less. The median diameter of the solid particles measured by dynamic light scattering is, for example, less than 1 μm. The solid particles have, for example, hydrophilic functional groups on their surfaces. In the recording medium, the recording layer includes, for example, 10 parts by mass or more and less than 70 parts by mass of a vinyl chloride polymer relative to 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles. In the recording medium, the recording layer includes, for example, 5 parts by mass or more and 40 parts by mass or less of a water-dispersed polymer relative to 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles. In the above recording medium, the recording layer contains, for example, 5 parts by mass or more and less than 50 parts by mass of solid particles per 100 parts by mass of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles combined.

[0014] In a sixth aspect of the present invention, a method for producing an aqueous dispersion is provided. The method includes, for example, a step of preparing a reaction liquid by mixing a vinyl chloride monomer, a water-dispersed polymer, solid particles, and an aqueous solvent. The method includes, for example, a step of polymerizing the vinyl chloride monomer in the presence of the water-dispersed polymer and the solid particles. In the method, the weight average molecular weight of the water-dispersed polymer is, for example, 5,000 to 50,000. In the method, the median diameter of the solid particles measured by a dynamic light scattering method is, for example, less than 1 μm. The solid particles have, for example, hydrophilic functional groups on their surfaces. In the method, the reaction liquid includes, for example, 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer relative to 100 parts by mass of the total of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles. In the method, the reaction liquid includes, for example, 5 parts by mass or more and 40 parts by mass or less of the water-dispersed polymer relative to 100 parts by mass of the total of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles. In the above method, the reaction liquid contains, for example, 5 parts by mass or more and less than 50 parts by mass of solid particles relative to 100 parts by mass in total of the vinyl chloride monomer, the water-dispersible polymer, and the solid particles.

[0015] In the above method, the step of polymerizing the vinyl chloride monomer comprises: (i) adjusting the concentration of the surfactant having a molecular weight of 1,000 or less in the reaction liquid to 100 g / m 3 The method may include a step of polymerizing vinyl chloride monomer under the following conditions: (i) the ratio of the mass of a surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride monomer is less than 0.001% by mass;

[0016] The above summary of the invention does not list all of the necessary features of the present invention. Also, subcombinations of these features may also be inventions. [Brief description of the drawings]

[0017] [Figure 1] An example of a recording medium 100 and a method for manufacturing the recording medium 100 are shown in schematic form. [Diagram 2]An example of a dispersoid 134 having a core-shell type structure is shown diagrammatically. [Diagram 3] An example of a method for producing the dispersion 130 is shown in schematic form. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The present invention will be described below through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. Not all of the combinations of features described in the embodiments are essential to the solution of the invention. In addition, the embodiments will be described with reference to the drawings, but in the description of the drawings, the same reference numbers may be used for the same or similar parts, and duplicate descriptions may be omitted.

[0019] (Outline of recording medium 100) 1 is a schematic diagram of an example of a recording medium 100 and a method for producing the same. In this embodiment, the recording medium 100 includes a substrate 110 and a recording layer 120, for example.

[0020] In this embodiment, the recording medium 100 is used to record various information such as characters, symbols, patterns, and figures. The above information is recorded on the surface or inside of the recording layer 120 of the recording medium 100 by means of printing, coating, or coating (sometimes simply referred to as coating). According to one embodiment, a receptive layer for fixing ink, paint, and the like is disposed on the surface of the recording layer 120. According to another embodiment, the recording layer 120 includes a receptive layer and another layer disposed on the receptive layer. Examples of the recording medium 100 include recording paper, labels, posters, wallpaper, and packaging materials. Examples of packaging materials include PET film, OPP film, and PP film.

[0021] (Outline of the substrate 110) In this embodiment, the substrate 110 supports, for example, the recording layer 120. Examples of materials constituting the substrate 110 include paper, fiber, leather, resin, metal, glass, cement, and wood. Examples of fibers include woven fabric, knitted fabric, and nonwoven fabric. The fibers may be natural fibers or synthetic fibers. Examples of the shape of the substrate 110 include a sheet or film shape, a plate shape, a column shape, or a block shape.

[0022] (Outline of recording layer 120) In this embodiment, the recording layer 120 is used to record various information such as characters, symbols, patterns, and figures. The recording layer 120 may be composed of a single layer or may be composed of multiple layers. The recording layer 120 may include a receiving layer. The recording layer 120 may function as the receiving layer.

[0023] In this embodiment, the recording layer 120 is disposed on at least one of the multiple surfaces of the substrate 110. In one embodiment, the substrate 110 and the recording layer 120 may be in contact with each other. In another embodiment, another material may be disposed between the substrate 110 and the recording layer 120.

[0024] In this embodiment, the recording layer 120 includes a composition derived from the dispersion 130. The recording layer 120 may have a receiving layer that includes a composition derived from the dispersion 130.

[0025] (Method of manufacturing the recording layer 120) The recording layer 120 is produced, for example, by the following procedure: First, the substrate 110 and the dispersion liquid 130 are prepared. Details of the substrate 110 may be as described above.

[0026] In this embodiment, the dispersion liquid 130 contains a vinyl chloride polymer (sometimes referred to as a vinyl chloride resin) and a water-dispersible polymer (sometimes referred to as a water-dispersible oligomer) having a weight average molecular weight of 5000 to 50000. The dispersion liquid 130 may contain, as a dispersoid, a core-shell structure constituted by the vinyl chloride polymer and the water-dispersible oligomer.

[0027] In this embodiment, the dispersion 130 contains solid particles having a median diameter (sometimes referred to as 50% particle diameter, D50, etc.) of less than 1 μm as determined by dynamic light scattering, as a stabilizer or aggregation inhibitor for dispersing the dispersoid in the dispersion medium. In dynamic light scattering, a particle size distribution is created based on the intensity of scattered light. Therefore, the particle size distribution initially obtained in dynamic light scattering is based on the scattered light intensity. A dispersion stabilized by solid particles may be called a Pickering emulsion. Details of the dispersion 130 will be described later.

[0028] Next, a paint 140 containing the dispersion liquid 130 is prepared. For example, the paint 140 is obtained by mixing the dispersion liquid 130 with any type of solvent in any ratio. The details of the paint 140 will be described later.

[0029] Next, the paint 140 is applied onto one surface of the substrate 110. The paint 140 is applied onto one surface of the substrate 110 by a coating method such as a blade coater, an air knife coater, a curtain coater, a Mayer bar coater, a gravure coater, or a roll coater. The amount of paint 140 applied is 3 to 25 g / m2 in terms of dry weight solid content. 2 This forms a paint layer 150 on one surface of the substrate 110.

[0030] Thereafter, the coating layer 150 is dried to produce the recording layer 120 containing the composition derived from the dispersion liquid 130. The drying temperature may be 50° C. or higher, and is preferably 100° C. or higher. In this way, the recording medium 100 including the substrate 110 and the recording layer 120 is produced.

[0031] (Composition of Dispersion 130) In this embodiment, the dispersion liquid 130 includes, for example, a dispersion medium 132, a dispersoid 134, and a stabilizer 136. The dispersion liquid 130 may be substantially free of an organic compound-based surfactant. The dispersion liquid 130 may be substantially free of a cationic surfactant and / or an amphoteric surfactant. The dispersion liquid 130 may be substantially free of a surfactant having a molecular weight of 1000 or less. For example, (i) the content of the above surfactant in the dispersion liquid 130 is 100 g / m 3 (sometimes referred to as ppm) or less, or (ii) when the ratio of the mass of the above surfactant to the mass of the vinyl chloride resin contained in dispersion 130 is less than 0.001 mass%, it can be determined that dispersion 130 is substantially free of the surfactant.

[0032] (Summary of Dispersion Medium 132) According to this embodiment, water or an aqueous solution of various substances is used as the dispersion medium 132. The dispersion medium 132 may contain a water-soluble organic solvent.

[0033] Examples of solutes in the aqueous solution used as the dispersion medium 132 include acrylic oligomers and urethane oligomers. The content of each solute in the dispersion medium 132 may be 2.5 wt% or more and less than 12.5 wt% of the acrylic oligomer, or 2.5 wt% or more and 12.5 wt% or less of the urethane oligomer.

[0034] Examples of water-soluble organic solvents include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol, etc. The content of each water-soluble organic solvent in the dispersion medium 132 may be 0.1 wt% or more and 10 wt% or less, or 1 wt% or more and 5 wt% or less.

[0035] (Summary of Dispersoid 134) In this embodiment, the dispersoid 134 includes, for example, the vinyl chloride resin described above and the water-dispersible oligomer described above. The vinyl chloride resin may be a homopolymer or a copolymer. In the dispersion medium 132, the water-dispersible oligomer is disposed, for example, so as to cover the vinyl chloride resin. The water-dispersible oligomer is disposed so as to surround the periphery of the polymer, thereby forming a particulate or colloidal composition. The dispersoid 134 may include a core-shell structure constituted by the vinyl chloride resin and the water-dispersible oligomer.

[0036] The core-shell structure is composed of, for example, at least a portion of the vinyl chloride resin contained in the dispersion liquid 130 and at least a portion of the water-dispersible oligomer contained in the dispersion liquid 130. The core-shell structure has, for example, a structure in which a shell made of a water-dispersible oligomer is disposed around a core made of a vinyl chloride resin.

[0037] In the core-shell structure according to this embodiment, the median diameter (sometimes referred to as 50% particle diameter, D50, etc.) measured by dynamic light scattering may be 10 to 600 nm. The median diameter measured by the dynamic light scattering method may be 20 to 500 nm, preferably 20 to 120 nm, and more preferably 20 to 100 nm. The details of the dispersoid 134 having the core-shell structure described above will be described later.

[0038] (Vinyl chloride resin) In this embodiment, the vinyl chloride resin may be (i) a homopolymer of a vinyl chloride monomer, or (ii) a copolymer of a vinyl chloride monomer and one or more ethylenically unsaturated group-containing monomers. The ethylenically unsaturated group-containing monomer may be any compound that can be copolymerized with the vinyl chloride monomer, and the details thereof are not particularly limited.

[0039] Examples of the ethylenically unsaturated group-containing monomer include ethylene, propylene, vinylidene chloride, vinyl carboxylate monomers, aromatic vinyl monomers, conjugated diene monomers, ethylenically unsaturated monocarboxylate esters, ethylenically unsaturated polycarboxylate esters, ethylenically unsaturated monocarboxylic acids, ethylenically unsaturated dicarboxylic acids, epoxy group-containing monomers, alcoholic hydroxyl group-containing monomers, alkoxyl group-containing monomers, nitrile group-containing monomers, amide group-containing monomers, and amino group-containing monomers. The ethylenically unsaturated group-containing monomer may be a monomer having two or more ethylenically unsaturated groups in one molecule. Of these monomers, vinyl acetate, ethylenically unsaturated monocarboxylate esters, and ethylenically unsaturated monocarboxylic acids can be preferably used.

[0040] Examples of vinyl carboxylate monomers include vinyl acetate, vinyl propionate, and derivatives thereof. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, and derivatives thereof. Examples of conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, and derivatives thereof.

[0041] Examples of ethylenically unsaturated monocarboxylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, and derivatives thereof. Examples of ethylenically unsaturated polycarboxylic acid esters include dimethyl itaconate, diethyl maleate, monobutyl maleate, monoethyl fumarate, dibutyl fumarate, and derivatives thereof.

[0042] Examples of ethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and derivatives thereof. Examples of ethylenically unsaturated dicarboxylic acids include itaconic acid, maleic acid, fumaric acid, and derivatives thereof. Examples of epoxy group-containing monomers include glycidyl methacrylate and derivatives thereof.

[0043] Examples of the alcoholic hydroxyl group-containing monomers include 2-hydroxyethyl methacrylate and its derivatives. Examples of the alkoxyl group-containing monomers include methoxyethyl acrylate and its derivatives. Examples of the nitrile group-containing monomers include acrylonitrile and its derivatives. Examples of the amide group-containing monomers include acrylamide and its derivatives. Examples of the amino group-containing monomers include dimethylaminoethyl methacrylate and its derivatives. Examples of the monomers having two or more ethylenically unsaturated groups in one molecule include divinylbenzene, allyl methacrylate, and their derivatives.

[0044] The ratio of the mass of the vinyl chloride monomer to the mass of the ethylenically unsaturated group-containing monomer is, for example, 50:50 to 100:0, and preferably 70:30 to 100:0. When the content of the vinyl chloride monomer is within the above numerical range, for example, the generation of aggregates during the production of the dispersion 130 or during the storage period of the dispersion 130 can be suppressed. The aggregates are, for example, a mixture of a vinyl chloride polymer and solid particles added to stabilize the dispersion. An example of the solid particles is silica.

[0045] (Water-dispersible oligomer) In this embodiment, the water-dispersed oligomer is a resin with a relatively low molecular weight and is configured to be dispersible in an aqueous solvent such as the dispersion medium 132. The water-dispersed oligomer is, for example, a polymer having a weight-average molecular weight of 5000 or more and 50000 or less, expressed as a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method. The water-dispersed oligomer may be a polymer having the above-mentioned weight-average molecular weight of 8000 or more and 25000 or less. When the weight-average molecular weight of the water-dispersed oligomer is within the above-mentioned numerical range, for example, the generation of aggregates during the production of the dispersion liquid 130 or during the storage period of the dispersion liquid 130 can be suppressed. The above-mentioned aggregates are, for example, a mixture of the water-dispersed oligomer and a vinyl chloride resin.

[0046] The water-dispersible oligomer includes, for example, at least one of a polymer of an ethylenically unsaturated group-containing monomer and a urethane-based polymer. The polymer of an ethylenically unsaturated group-containing monomer may be a homopolymer consisting essentially of a single type of monomer unit, or may be a copolymer containing a plurality of types of monomer units. Examples of the polymer of an ethylenically unsaturated group-containing monomer include an acrylic acid ester oligomer and a styrene-acrylic acid ester oligomer. Examples of the urethane-based polymer include a polycarbonate-based urethane oligomer and a polyester-based urethane oligomer.

[0047] The acrylic acid ester oligomer may be a homopolymer or copolymer of a (meth)acrylic acid ester monomer. The styrene-acrylic acid ester oligomer may be a copolymer of a styrene-based monomer and a (meth)acrylic acid ester monomer. Examples of the (meth)acrylic acid ester monomer include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. The term (meth)acrylic is used as a general term for acrylic and methacrylic. Examples of the acrylic acid ester oligomer or styrene-acrylic acid ester oligomer include JONCRYL JDX-6500 (manufactured by BASF Japan Ltd.), JONCRYL JDX-6102B (manufactured by BASF Japan Ltd.), JONCRYL HPD-96J (manufactured by BASF Japan Ltd.), and JONCRYL 52J (manufactured by BASF Japan Ltd.).

[0048] The polycarbonate-based urethane oligomer may be a homopolymer or copolymer of a polycarbonate-based diol monomer. Examples of the polycarbonate-based urethane oligomer include ETERNACALL UW-1005E (manufactured by UBE Corporation), HYDRAN WLS-207 (manufactured by DIC Corporation), and HYDRAN WLS-230 (manufactured by DIC Corporation).

[0049] The water-dispersible oligomer may include at least one of an acrylic acid ester oligomer, a styrene-acrylic acid ester oligomer, and a polycarbonate-based urethane oligomer. The water-dispersible oligomer may include at least one of an acrylic acid ester oligomer, a styrene-acrylic acid ester oligomer, and a polycarbonate-based urethane oligomer. The water-dispersible oligomer may include an acrylic acid ester oligomer and / or a polycarbonate-based urethane oligomer.

[0050] The water-dispersible oligomer may have at least one of a carboxy group and a urethane group, which allows the water-dispersible oligomer to be configured to be dispersible in an aqueous solvent.

[0051] The water-dispersed oligomer may be substantially free of the monomer units derived from the vinyl chloride monomer described above. The proportion of the monomer units derived from the vinyl chloride monomer contained in the water-dispersed oligomer may be less than 0.1 wt%.

[0052] (Summary of Stabilizer 136) In this embodiment, the stabilizer 136 suppresses aggregation or coalescence of the dispersoid 134 in the dispersion medium 132. This improves the dispersibility or dispersion stability of the dispersoid 134. In this embodiment, the stabilizer 136 includes, for example, solid particles having a median diameter of less than 1 μm as measured by a dynamic light scattering method. The above solid particles may be used as the stabilizer 136.

[0053] The median diameter of the solid particles measured by dynamic light scattering may be less than 500 nm or less than 300 nm. The median diameter of the solid particles measured by dynamic light scattering may be 6 nm or more and 100 nm or less, or 6 nm or more and 80 nm or less.

[0054] When the size of the solid particles is equal to or larger than the lower limit of the above-mentioned range, an increase in the viscosity of the dispersion 130 is suppressed, and a dispersion 130 having a viscosity suitable for use as a paint or water-based ink is obtained. When the size of the solid particles is equal to or smaller than the upper limit of the above-mentioned range, settling of the dispersoid 134 can be appropriately suppressed.

[0055] As described above, in this embodiment, water or an aqueous solution of various substances is used as the dispersion medium 132. In this case, the stabilizer 136 may include solid particles having a median diameter of less than 1 μm as measured by dynamic light scattering and having hydrophilic functional groups on their surfaces. Examples of hydrophilic functional groups include hydroxyl groups and carboxyl groups. The above solid particles may be used as the stabilizer 136.

[0056] Examples of the solid particles include (i) inorganic fine particles having hydrophilic functional groups on the surface thereof, (ii) organic fine particles whose surfaces have been modified or altered to be hydrophilic, etc. The solid particles may be colloidal silica, carbon black and / or cellulose-based particles.

[0057] The solid particles may be colloidal silica having a median diameter of 6 nm to 100 nm as measured by dynamic light scattering. The median diameter of the colloidal silica as measured by dynamic light scattering may be 6 nm to 80 nm. The colloidal silica may be obtained, for example, by heating and aging a silica sol. The silica sol may be obtained, for example, by subjecting a product of a double decomposition treatment of sodium silicate and an acid to an ion exchange treatment using an ion exchange resin.

[0058] The colloidal silica may be colloidal silica stabilized in a basic or neutral range. Examples of colloidal silica stabilized in a basic range include colloidal silica stabilized with ammonia, a sodium compound, a potassium compound, a calcium compound, and / or aluminum hydroxide. The colloidal silica may be colloidal silica stabilized with ammonia or colloidal silica stabilized with a sodium compound.

[0059] Examples of the colloidal silica include "Snowtex Series" manufactured by Nissan Chemical Industries, Ltd., "Ludox Series" manufactured by WR Grace Japan, and "PL Series" manufactured by Fuso Chemical Co., Ltd. One or more types of colloidal silica may be used as the solid particles.

[0060] According to the present embodiment, the solid particles are adsorbed, coordinated, or attached to the interface between the dispersion medium 132 and the dispersoid 134, thereby preventing the dispersoid 134 from aggregating or coalescing in the dispersion medium 132. This makes it possible to prepare a dispersion 130 or a paint 140 that is substantially free of a surfactant.

[0061] According to this embodiment, at least a part of the solid particles added to the dispersion liquid 130 as the stabilizer 136 is bound to the water-dispersed oligomer constituting the above-mentioned core-shell structure by intermolecular interaction. At least a part of the solid particles may be adsorbed to the water-dispersed oligomer constituting the above-mentioned core-shell structure. At least a part of the solid particles may be attached to the water-dispersed oligomer constituting the above-mentioned core-shell structure in a form other than a covalent bond. At least a part of the solid particles may be attached to the water-dispersed oligomer constituting the above-mentioned core-shell structure in a form other than a chemical bond. The above-mentioned solid particles are, for example, arranged on the outermost shell of the core-shell structure.

[0062] Examples of intermolecular interactions include electrostatic interactions, van der Waals interactions, interactions due to hydrogen bonds, interactions similar to hydrogen bonds, etc. Examples of interactions similar to hydrogen bonds include interactions between hydrogen atoms and π electrons, interactions between π electrons, interactions via coordinate bonds, interactions caused by the transfer of electrons between molecules (sometimes referred to as charge transfer interactions), etc.

[0063] (Other additives) The dispersion liquid 130 may contain various additives, for example, within a range that does not impair the alcohol resistance and / or flexibility of the composition derived from the dispersion liquid 130. Examples of the additives include a polymerization aid, a plasticizer, an inorganic filler, an organic filler, a thickener, and the like that are added in the manufacturing process of the dispersion liquid 130. Examples of the polymerization aid include an emulsifier, a polymerization initiator, a chain transfer agent, a pH adjuster, an antifoaming agent, a surfactant, and the like.

[0064] Examples of emulsifiers include alkyl sulfates, examples of chain transfer agents include mercaptans, and examples of pH adjusters include sodium carbonate.

[0065] Examples of the surfactant include nonionic surfactants, anionic surfactants, etc. Specific examples of the surfactant include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, glycerin fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, or acetylene alcohols, acetylene glycols, and their ethylene oxide adducts.

[0066] As described above, the dispersion 130 may be substantially free of organic compound-based surfactants. The dispersion 130 may be substantially free of cationic surfactants and / or amphoteric surfactants, and may be substantially free of surfactants having a molecular weight of 1000 or less. This improves the water resistance and alcohol resistance of the composition derived from the dispersion 130.

[0067] Examples of the polymerization initiator include persulfates, azo compounds, peroxides, tartaric acid, redox initiators, etc. Examples of the persulfates include ammonium persulfate and potassium persulfate. Examples of the azo compounds include 2,2'-diamidino-2,2'-azopropane dihydrochloride and azobisisobutyronitrile. Examples of the peroxides include cumene hydroperoxide, benzoyl peroxide, and hydrogen peroxide. Examples of the redox initiators include potassium persulfate and sodium hydrogen sulfite.

[0068] (Composition ratio of each component in dispersion 130) In this embodiment, the dispersion liquid 130 contains the vinyl chloride resin, the water-dispersible oligomer, and the solid particles. For example, the dispersion liquid 130 contains 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride resin, 5 parts by mass or more and less than 40 parts by mass of the water-dispersible oligomer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles, relative to a total of 100 parts by mass of the vinyl chloride resin, the water-dispersible oligomer, and the solid particles. This provides the dispersion liquid 130 that is particularly suitable as a raw material for inks, paints, binders for dispersing inorganic substances, recording layers of recording media, fiber treatment agents, various coatings, and the like.

[0069] For example, the synthetic resin emulsions described in Patent Documents 1 to 5 do not contain solid particles that function as the stabilizer 136. Therefore, the water-based inks prepared using the synthetic resin emulsions described in Patent Documents 1 to 5 have room for improvement in terms of print bleeding, blocking resistance, and alcohol resistance. Similarly, the recording media having a recording layer prepared using the synthetic resin emulsions described in Patent Documents 1 to 5 have room for improvement in terms of print bleeding, blocking resistance, flexibility, and alcohol resistance of the recording layer.

[0070] For example, the synthetic resin emulsion described in Patent Document 6 contains a surfactant in addition to silica microparticles. Therefore, it has poor water resistance. The synthetic resin emulsion described in Patent Document 7 contains a reactive anion emulsifier. Therefore, it has poor water resistance. The synthetic resin emulsion described in Patent Document 8 has a small amount of vinyl chloride polymer content, so it has poor alcohol resistance. The synthetic resin emulsion described in Patent Document 9 has a low solid content, so it is difficult to achieve flexibility.

[0071] In contrast, the dispersion 130 having the above composition is used as a raw material for ink, paint, binder for dispersing inorganic substances, recording layer of recording medium, treatment agent for fibers, various coatings, etc., to obtain a product having excellent coatability, water resistance, alcohol resistance, abrasion resistance, sliding property, and / or flexibility of the coating film derived from the dispersion 130. According to one embodiment, for example, an aqueous ink having excellent water resistance, moisture resistance, color visibility, glossiness, and / or alcohol resistance is obtained. In particular, an aqueous ink having excellent alcohol resistance is obtained. According to another embodiment, for example, a recording medium having a recording layer having excellent color development, glossiness, water resistance, moisture resistance, flexibility, and / or alcohol resistance is obtained. In particular, a recording medium having a recording layer having excellent alcohol resistance and / or flexibility is obtained.

[0072] In this embodiment, the mass ratio of the vinyl chloride resin to the total mass of the vinyl chloride resin, the water-dispersed oligomer, and the solid particles may be 10% by mass or more and less than 70% by mass. The above ratio may be 10% by mass or more and 69% by mass or less, and is preferably 25% by mass or more and 65% by mass or less. When the above ratio is within the above numerical range, for example, the polymerization stability of the vinyl chloride resin in the manufacturing process of the dispersion 130 is improved.

[0073] In this embodiment, the ratio of the mass of the water-dispersed oligomer to the total mass of the vinyl chloride resin, the water-dispersed oligomer, and the solid particles may be 5% by mass or more and 40% by mass or less. The ratio may be 10% by mass or more and 35% by mass or less, and is preferably 20% by mass or more and 30% by mass or less. When the ratio is equal to or more than the lower limit of the above numerical range, for example, the generation of aggregates in the dispersion 130 can be suppressed. When the ratio is equal to or less than the upper limit of the above numerical range, for example, the dispersion 130 having excellent stability over time can be obtained. In addition, the polymerization stability of the vinyl chloride resin in the manufacturing process of the dispersion 130 is improved.

[0074] In this embodiment, the ratio of the mass of the solid particles to the total mass of the vinyl chloride resin, the water-dispersed oligomer, and the solid particles may be 5% by mass or more and less than 50% by mass. The ratio may be 5% by mass or more and 49% by mass or less, and is preferably 5% by mass or more and 45% by mass or less. When the ratio is equal to or more than the lower limit of the above numerical range, for example, the composition derived from the dispersion 130 exhibits excellent alcohol resistance. When the ratio is less than the upper limit of the above numerical range, the dispersion 130 having excellent film-forming properties is obtained. In addition, the polymerization stability of the vinyl chloride resin in the manufacturing process of the dispersion 130 is improved.

[0075] The ratio of the mass of the water-dispersible oligomer to the mass of the vinyl chloride resin may be 5% by mass or more and 700% by mass or less. The ratio may be 10% by mass or more and 200% by mass or less, and is preferably 30% by mass or more and 100% by mass or less.

[0076] The ratio of the mass of the solid particles to the mass of the vinyl chloride resin may be 0.1% by mass or more and 700% by mass or less. The ratio may be 1% by mass or more and 300% by mass or less, and is preferably 5% by mass or more and 150% by mass or less.

[0077] The ratio of the mass of the solid particles to the mass of the water-dispersible oligomer may be 0.1% by mass or more and 5000% by mass or less. The ratio may be 5% by mass or more and 400% by mass or less, and is preferably 10% by mass or more and 300% by mass or less.

[0078] In this embodiment, the ratio of the mass of the solid content contained in the dispersion 130 to the mass of the dispersion 130 may be 10% by mass or more and 50% by mass or less. The above ratio may be 20% by mass or more and 40% by mass or less, and is preferably 25% by mass or more and 30% by mass or less. The mass of the solid content may be the total mass of the vinyl chloride resin, the water-dispersible oligomer, and the solid particles. When the above ratio is equal to or more than the lower limit of the above numerical range, the dispersion 130 having one or more of the above-mentioned effects is obtained. When the above ratio is equal to or less than the upper limit of the above numerical range, for example, gelation of the dispersion 130 may be suppressed.

[0079] (Physical properties of dispersion 130) The viscosity of the dispersion 130 may be 1 to 1800 mPa·s in the temperature range of 22.5° C. or more and 23.5° C. or less. The viscosity of the dispersion 130 may be 1 to 1000 mPa·s, and is preferably 1 to 500 mPa·s, in the above temperature range. The viscosity of the dispersion 130 is measured, for example, using a B-type viscometer (Toki Sangyo TVB-10M, No. 1 rotor, 6 rpm). The viscosity of the dispersion 130 is measured, for example, in accordance with JIS K-7117-1:1999.

[0080] The median diameter of the dispersoid 134 contained in the dispersion 130, as measured by a dynamic light scattering method, may be 10 nm or more and 600 nm or less. The median diameter, as measured by the dynamic light scattering method, may be 20 nm or more and 500 nm or less, preferably 20 nm or more and 120 nm or less, and more preferably 20 nm or more and 100 nm or less.

[0081] (Paint 140 composition) As described above, the paint 140 contains the dispersion liquid 130. The ratio of the mass of the solid content contained in the dispersion liquid 130 to the mass of the paint 140 may be 2 mass% or more and 30 mass% or less. The above ratio is preferably 5 mass% or more and 20 mass% or less. The mass of the solid content may be the total mass of the vinyl chloride resin, the water-dispersible oligomer, and the solid particles.

[0082] The paint 140 may contain (a) the dispersion liquid 130 and (b) at least one of a colorant and a solvent. Examples of the colorant include pigments and dyes. Examples of the solvent include water, aqueous solutions of various substances, and water-soluble organic solvents. The paint 140 may further contain additives such as pigment dispersants, leveling agents, defoamers, colorants, antioxidants, ultraviolet absorbers, viscosity modifiers, and release agents. These additives are used, for example, in amounts normally used in aqueous inks.

[0083] Examples of the water-soluble organic solvent include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, acetone, ethyl acetate, and diacetone alcohol. The mass ratio of the water-soluble organic solvent to the mass of the paint 140 may be 0 to 60 mass%, and is preferably 0 to 50 mass%. When water is used as the solvent, the mass ratio of water to the mass of the paint 140 may be 5 to 95 mass%, and is preferably 10 to 90 mass%.

[0084] Examples of pigments include amorphous synthetic silica, aluminum silicate, magnesium silicate, precipitated calcium carbonate, heavy calcium carbonate, calcium silicate, aluminum hydroxide, zeolite, calcined clay, kaolin clay, talc, white carbon, etc. The ratio of the mass of the pigment to the mass of the paint 140 may be 10 to 90% by mass, and is preferably 20 to 80% by mass.

[0085] In this embodiment, the paint 140 may be substantially free of an organic compound-based surfactant. The paint 140 may be substantially free of a cationic surfactant and / or an amphoteric surfactant. The paint 140 may be substantially free of a surfactant having a molecular weight of 1000 or less. For example, the content of the surfactant in the paint 140 may be 100 ppm or less or 100 g / m 3 (sometimes referred to as ppm) or less, it can be determined that the paint 140 is substantially free of the surfactant.

[0086] As described above, the coating material 140 is dried to form the recording layer 120. This results in the recording layer 120 containing the vinyl chloride resin, the water-dispersible oligomer, and the solid particles. The recording layer 120 contains, for example, 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride resin, 5 parts by mass or more and less than 40 parts by mass of the water-dispersible oligomer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles (i.e., particles having a median diameter of less than 1 μm as measured by dynamic light scattering) relative to a total of 100 parts by mass of the vinyl chloride resin, the water-dispersible oligomer, and the solid particles.

[0087] The dispersion 130 may be an example of an aqueous dispersion. The dispersion medium 132 may be an example of an aqueous solvent. The dispersoid 134 may be an example of a core-shell structure. The stabilizer 136 may be an example of a solid particle. The paint 140 may be an example of a water-based ink.

[0088] (An example of another embodiment) In this embodiment, the details of the recording medium 100 are described by taking as an example a case where the recording medium 100 includes the substrate 110 and the recording layer 120. However, the recording medium 100 is not limited to this embodiment. In other embodiments, the recording medium 100 may include other layers. The other layers are disposed, for example, between the substrate 110 and the recording layer 120. When the recording layer 120 is disposed on the first surface side of the substrate 110, the other layers may be disposed on the second surface of the substrate 110. The second surface of the substrate 110 may be a surface different from the first surface of the substrate 110. When the substrate 110 is disposed on the first surface side of the recording layer 120, the other layers may be disposed on the second surface of the recording layer 120. The second surface of the recording layer 120 may be a surface different from the first surface of the recording layer 120.

[0089] In this embodiment, the details of the dispersion liquid 130 and the paint 140 have been described by taking as an example a case where the paint 140 is used to produce the recording layer 120. However, the dispersion liquid 130 and / or the paint 140 are not limited to this embodiment. In other embodiments, the paint 140 may be a vinyl chloride-based water-based ink, and the dispersion liquid 130 may be used as a binder for the vinyl chloride-based water-based ink.

[0090] (Outline of core-shell structure) The above-mentioned core-shell structure will be described in detail with reference to Fig. 2. Fig. 2 shows a schematic diagram of an example of a dispersoid 134 having a core-shell structure. Fig. 2 shows a schematic diagram of an example of a state in which the dispersoid 134 is dispersed in a dispersion medium 132.

[0091] 2, in this embodiment, the dispersoid 134 includes a core 210 and one or more water-dispersible oligomers 220 disposed on the outside of the core 210. The core 210 includes one or more vinyl chloride resins 212. Each of the one or more water-dispersible oligomers 220 is disposed so as to cover at least a portion of the core 210. The one or more water-dispersible oligomers 220 may be referred to as a shell.

[0092] According to this embodiment, the solid particles functioning as the stabilizer 136 are bound by intermolecular interactions to one or more water-dispersible oligomers 220 constituting the shell of the dispersoid 134. The solid particles are, for example, adsorbed, coordinated or attached to the interface between the dispersion medium 132 and the dispersoid 134, thereby stabilizing the dispersion 130.

[0093] The vinyl chloride resin 212 may be an example of a vinyl chloride polymer. The water-dispersible oligomer 220 may be an example of a water-dispersible polymer.

[0094] (Method of producing dispersion 130) 3 is a schematic diagram showing an example of a method for producing the dispersion 130. As described above, the dispersion 130 can be obtained, for example, by polymerizing the above-mentioned monomers in a reaction liquid obtained by mixing (i) one or more monomers that are structural units of the vinyl chloride resin described above, (ii) the water-dispersible oligomer described above, (iii) solid particles that function as the stabilizer 136 described above, and (iv) an aqueous solvent.

[0095] In one embodiment, when the vinyl chloride resin is a homopolymer, the reaction liquid is obtained by, for example, mixing the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles with an aqueous solvent. The reaction liquid is adjusted to contain, for example, 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer, 5 parts by mass or more and less than 40 parts by mass of the water-dispersed oligomer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles, relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles. In the reaction liquid, the amount of the vinyl chloride monomer added may be 10 parts by mass or more and 69 parts by mass or less, relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles.

[0096] In this embodiment, the ratio of the mass of the vinyl chloride monomer to the total mass of the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles may be 10% by mass or more and less than 70% by mass. The ratio may be 10% by mass or more and 69% by mass or less, and is preferably 25% by mass or more and 65% by mass or less. When the ratio is within the above numerical range, for example, the polymerization stability of the vinyl chloride resin in the manufacturing process of the dispersion 130 is improved.

[0097] In another embodiment, when the vinyl chloride resin is a copolymer, the reaction liquid is obtained by, for example, mixing a vinyl chloride monomer, an ethylenically unsaturated group-containing monomer copolymerizable with the vinyl chloride monomer, a water-dispersed oligomer, and solid particles with an aqueous solvent. The reaction liquid is adjusted to contain, for example, 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer, 5 parts by mass or more and less than 10 parts by mass of the ethylenically unsaturated group-containing monomer copolymerizable with the vinyl chloride monomer, 5 parts by mass or more and less than 40 parts by mass of the water-dispersed oligomer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles, relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles. In the reaction liquid, the amount of the vinyl chloride monomer added may be 10 parts by mass or more and 69 parts by mass or less, relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed oligomer, and the solid particles.

[0098] In this embodiment, the ratio of the total mass of the vinyl chloride monomer and the ethylenically unsaturated group-containing monomer to the total mass of the vinyl chloride monomer, the ethylenically unsaturated group-containing monomer, the water-dispersed oligomer, and the solid particles may be 10% by mass or more and less than 70% by mass. The ratio may be 10% by mass or more and 69% by mass or less, and is preferably 25% by mass or more and 65% by mass or less. When the ratio is within the above numerical range, for example, the polymerization stability of the vinyl chloride resin in the manufacturing process of the dispersion 130 is improved.

[0099] 3, according to this embodiment, first, in step 322 (the step may be abbreviated as S), the above-mentioned dispersion medium 132 is prepared. Also, a core-forming monomer and a shell-forming polymer to be used in generating the dispersoid 134 are prepared. Furthermore, the above-mentioned solid particles are prepared as the stabilizer 136.

[0100] The core-forming monomer may be the vinyl chloride monomer described above, or a mixture of the vinyl chloride monomer and an ethylenically unsaturated group-containing monomer described above. The shell-forming polymer may be the water-dispersible oligomer described above.

[0101] Next, in S324, the dispersion medium 132, the core-forming monomer, the shell-forming polymer, and the stabilizer 136 are mixed to prepare a reaction liquid. According to one embodiment, 10 parts by mass or more and less than 70 parts by mass of the core-forming monomer, 5 parts by mass or more and less than 40 parts by mass of the shell-forming polymer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles are added to the dispersion medium 132 relative to a total of 100 parts by mass of the core-forming monomer, the shell-forming polymer, and the solid particles. By thoroughly mixing these, the reaction liquid is prepared. According to another embodiment, 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer, 5 parts by mass or more and less than 40 parts by mass of the water-dispersible oligomer, and 5 parts by mass or more and less than 50 parts by mass of the solid particles are added to the dispersion medium 132 relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersible oligomer, and the solid particles. By thoroughly mixing these, the reaction liquid is prepared.

[0102] The amount of dispersion medium 132 added is adjusted, for example, so that the solids concentration in the reaction liquid is 10% by mass or more and 50% by mass or less. The amount of dispersion medium 132 added may be adjusted so that the solids concentration in the reaction liquid is 20% by mass or more and 40% by mass or less. As described above, the reaction liquid may be substantially free of an organic compound-based surfactant. In addition, the reaction liquid may be substantially free of a cationic surfactant and / or an amphoteric surfactant. The reaction liquid may be substantially free of a surfactant having a molecular weight of 1000 or less.

[0103] Next, in S326, a process for initiating a polymerization reaction of the core-forming monomer is carried out. For example, the reaction liquid is heated, and after the temperature of the reaction liquid reaches a predetermined temperature, the above-mentioned polymerization initiator is added to the reaction liquid. The above-mentioned predetermined temperature may be 40° C. or more and 80° C. or less, and preferably 50° C. or more and 70° C. or less. The ratio of the amount of the polymerization initiator added to the mass of the core-forming monomer may be 0.1% by mass or more and 2.0% by mass or less, and preferably 0.2% by mass or more and 1.0% by mass or less.

[0104] This allows the polymerization reaction of the core-forming monomer to proceed in the reaction solution. According to this embodiment, the polymerization reaction of the core-forming monomer proceeds in the presence of the water-dispersed oligomer and the above-mentioned solid particles. As a result, the dispersoid 134 having the above-mentioned core-shell structure is produced.

[0105] After it is confirmed that the polymerization of the core-forming monomer has progressed sufficiently, a process for terminating the polymerization reaction of the core-forming monomer is carried out, thereby producing a dispersion liquid 130.

[0106] The polymerization conditions and / or polymerization process of the core-forming monomer may be the same as those of known vinyl chloride resins. The core-forming monomer and various polymerization aids may be added all at once, in portions, or continuously at the beginning of the polymerization. The polymerization time may be 10 hours or more and 15 hours or less. The polymerization reaction may be carried out under an inert gas atmosphere such as nitrogen gas. After the polymerization is completed, any plasticizer, inorganic filler, organic filler, thickener, etc. may be added.

[0107] In one embodiment, the polymerization reaction of the core-forming monomer proceeds in the presence of an organic compound-based surfactant. In another embodiment, the polymerization reaction of the core-forming monomer proceeds in a reaction solution that is substantially free of an organic compound-based surfactant. In this case, the polymerization conditions and / or polymerization process can be determined by a procedure similar to that of known soap-free polymerization or Pickering polymerization. For example, the step of polymerizing the core-forming monomer includes the steps of: (i) setting the concentration of a surfactant having a molecular weight of 1000 or less in the reaction solution to 100 g / m 3 The method includes a step of polymerizing a core-forming monomer under the following conditions: (i) the ratio of the mass of a surfactant having a molecular weight of 1000 or less to the mass of the core-forming monomer is less than 0.001 mass %. EXAMPLES

[0108] The present invention will be described in detail below with reference to examples. Note that the present invention is not limited to the following production examples, synthesis examples, or examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0109] Example 1 After the inside of a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet was replaced with nitrogen, 1050 parts of deionized water, 280 parts of vinyl chloride, 350 parts by mass of JONCRYL JDX-6500 (manufactured by BASF, acrylic oligomer as active ingredient: 30%), and 1050 parts by mass of Snowtex S (manufactured by Nissan Chemical Co., Ltd., solid content SiO2 as active ingredient: 30%, particle size 9 nm) were charged into the polymerization vessel. The composition of the raw materials for the aqueous dispersion is shown in Table 1.

[0110] JONCRYL JDX-6500 is an acrylic oligomer with a weight average molecular weight of 10,000. Snowtex S is a sodium-stable colloidal silica with a pH of 9.5 to 10.0. The median diameter of the colloidal silica contained in Snowtex S is 9 nm as measured by dynamic light scattering.

[0111] While stirring the raw materials (sometimes referred to as reaction liquid) charged inside the polymerization vessel, the reaction liquid was heated until the temperature of the reaction liquid reached 60°C. After confirming that the temperature of the reaction liquid had reached 60°C, a solution obtained by dissolving 4 parts of ammonium persulfate in 50 parts of deionized water was added to the reaction liquid as a polymerization initiator. When the internal pressure of the polymerization vessel reached 0.1 MPa, the residual monomer was removed in a vacuum to 1000 ppm, and then cooled to 40°C or less. Then, 10 parts of 25% ammonia water was added to the reaction liquid. As a result, an aqueous dispersion of polyvinyl chloride resin was obtained.

[0112] Considering the characteristics of the vinyl chloride resin, the acrylic oligomer, and the colloidal silica, it was presumed that a core-shell structure was formed in the aqueous dispersion, in which the acrylic oligomer was arranged so as to cover the vinyl chloride resin, and that a part of the colloidal silica was bonded, adsorbed, or attached to the surface of the core-shell structure.

[0113] Thereafter, the physical properties of the obtained aqueous dispersion were measured. Specifically, the solids concentration, pH, and viscosity of the aqueous dispersion were measured by the following procedures. In addition, the median diameter of the particles dispersed in the aqueous dispersion was measured by dynamic light scattering. The measurement results regarding the physical properties of the aqueous dispersion and the particles are shown in Table 1.

[0114] (solid content concentration) First, an aluminum foil dish with a diameter of 70 mm and a depth of 12 mm was prepared. The mass A (g) of the aluminum foil dish was measured. Next, about 1 g of the aqueous dispersion obtained in Example 1 was poured into the aluminum foil dish. The mass W (g) of the dish containing the aqueous dispersion was measured. Next, the dish containing the aqueous dispersion was left in a dryer for 1 hour to evaporate the water contained in the aqueous dispersion. The temperature of the dryer was maintained at 105 to 110°C. Next, the aluminum foil dish was removed from the dryer and allowed to cool in a desiccator. The mass D (g) of the aluminum foil dish after cooling was measured.

[0115] The solid content concentration R (%) was calculated by the following formula (1). The solid content concentration in the aqueous dispersion was 25 mass %. (Formula 1) R = (DA) / (WA) x 100

[0116] (pH) The pH of the aqueous dispersion was measured according to JIS Z8802 (pH measurement method). A glass electrode type hydrogen ion concentration indicator (Model D-55, manufactured by Horiba, Ltd.) was used to measure the pH. The pH of the aqueous dispersion was 9.4.

[0117] (viscosity) The viscosity of the aqueous dispersion was measured using a B-type viscometer (Toki Sangyo TVB-10M, No. 1 rotor, 6 rpm). During the measurement period, the temperature of the aqueous dispersion was maintained at 22.5°C or higher and 23.5°C or lower. The viscosity of the aqueous dispersion was 5 mPa s.

[0118] (Median diameter by dynamic light scattering method) A light scattering type particle size measuring device (ELSZ-2000ZS, manufactured by Otsuka Electronics) was used to measure the median diameter of the particles contained in the aqueous dispersion obtained in Example 1 by dynamic light scattering. Specifically, first, a sample of the aqueous dispersion was collected in a plastic container, and the aqueous dispersion was diluted 1000 times with pure water at 25°C. Next, the diluted sample was set in the light scattering type particle size measuring device. Next, it was confirmed that the concentration of the sample was within the appropriate concentration range, and the measurement of the particle size was started under the conditions of a measurement liquid temperature of 25°C, an accumulation number of 25 times, and a measurement number of 1 time. The median diameter of the particles dispersed in the aqueous dispersion was 23.6 nm.

[0119] (evaluation) Next, the properties of the aqueous dispersion and the properties of the coating film obtained by applying and drying the aqueous dispersion were evaluated according to the following procedure. Specifically, the stability of the aqueous dispersion was evaluated as the property of the aqueous dispersion. In addition, the coatability, water resistance, alcohol resistance, pencil hardness, and dynamic friction coefficient of the coating film were evaluated as the property of the coating film. The evaluation results of the aqueous dispersion and the coating film are shown in Table 4.

[0120] (Stability of aqueous dispersion) After preparing the aqueous dispersion, the aqueous dispersion was left to stand for one month. After that, the aqueous dispersion was filtered using a 300 mesh filter cloth, and the presence or absence of aggregates on the filter cloth was visually confirmed. In Table 4, ○ indicates that no aggregates were observed. × indicates that aggregates were observed or that gelation of the aqueous dispersion was observed.

[0121] (Coatability of coating film) The aqueous dispersion obtained in Example 1 was applied to the surface of a PET film (Torel Lumirror L-75) using a bar coater No. 10. The PET film coated with the aqueous dispersion was dried at 105° C. for 300 seconds. This resulted in a coating of the aqueous dispersion of Example 1.

[0122] The appearance of the coating film produced by the above procedure was observed visually and with a microscope (manufactured by Keyence Corporation) to confirm the state of coating film formation and the degree of circular depressions called repelling (cissing or cratering). Based on the above observation results, the coatability of the coating film was evaluated as follows. In Table 4, ○ indicates that the wettability to the substrate was good and a continuous film was formed. △ indicates that the wettability to the substrate was poor or a continuous film was not formed. × indicates that the wettability to the substrate was poor and a continuous film was not formed.

[0123] (Water resistance of coating film: Droplet test) A drop of pure water was placed on the coating film prepared by the above procedure and left for 1 minute. After wiping off the pure water on the coating film, the state of the coating film was observed. Based on the above observation results, the water resistance of the coating film was evaluated as follows. In Table 4, ○ indicates that no whitening or dissolution of the coating film was observed and the coating film remained transparent. △ indicates that slight whitening was observed in the coating film and the coating film changed to a translucent state. × indicates that whitening or dissolution of the coating film was observed.

[0124] (Water resistance of coating film: Scratch test) A cotton swab moistened with pure water was rubbed on the coating film prepared by the above procedure, and the cotton swab was moved back and forth 10 times. The condition of the coating film was visually observed, and the ratio (%) of the area of ​​the part where no abnormality was observed in the coating film to the area of ​​the part rubbed with the cotton swab was calculated. If whitening or peeling of the coating film was observed, the condition of the coating film was determined to be abnormal.

[0125] (Alcohol resistance of coating film: Droplet test) A droplet test was carried out with different ethanol concentrations. Specifically, a droplet test was carried out when the ethanol concentration was 80% by mass, and a droplet test was carried out when the ethanol concentration was about 100% (for example, anhydrous ethanol with an ethanol concentration of 99.5% by mass or more).

[0126] The droplet test was carried out according to the following procedure. First, a drop of ethanol was placed on the coating film prepared by the above procedure and left for 1 minute. After wiping off the ethanol on the coating film, the state of the coating film was observed. Based on the observation results, the water resistance of the coating film was evaluated as follows. In Table 4, ○ indicates that no whitening or dissolution of the coating film was observed and the coating film remained transparent. △ indicates that slight whitening was observed in the coating film and the coating film changed to semi-transparent. × indicates that whitening or dissolution of the coating film was observed.

[0127] (Alcohol resistance of coating film: Scratch test) A rubbing test was carried out with different ethanol concentrations. Specifically, a rubbing test was carried out when the ethanol concentration was 80% by mass, and a rubbing test was carried out when the ethanol concentration was about 100% (for example, anhydrous ethanol with an ethanol concentration of 99.5% by mass or more).

[0128] The scratch test was carried out according to the following procedure. First, a cotton swab moistened with ethanol was rubbed on the coating film prepared by the above procedure, and the cotton swab was moved back and forth 10 times. The condition of the coating film was visually observed, and the ratio (%) of the area of ​​the portion where no abnormality was observed in the coating film to the area of ​​the portion rubbed with the cotton swab was calculated. If whitening or peeling of the coating film was observed, the condition of the coating film was determined to be abnormal.

[0129] (Pencil hardness of coating film) The pencil hardness of the coating film prepared by the above procedure was measured according to JIS K5600-5-4 (pencil scratch test). When the pencil hardness of the coating film was H or less, it was determined that the coating film had excellent flexibility.

[0130] (Dynamic friction coefficient of coating film) The dynamic friction coefficient of the coating film prepared by the above procedure was measured using a friction and wear tester (HEIDON TYPE-38, manufactured by Shinto Scientific Co., Ltd.). Specifically, the metal indenter of the friction and wear tester was brought into contact with the coating film perpendicularly, and the friction force was measured when the metal indenter was moved at a speed of 3 cm / min. The mass of the metal indenter was 30 g. The friction coefficient was calculated based on the measurement results of the friction force. When the dynamic friction coefficient of the coating film was less than 0.50, it was determined that the coating film had excellent sliding properties.

[0131] (Examples 2 to 3) Except for changing the composition ratio of the raw materials, the aqueous dispersion was prepared in the same manner as in Example 1. The physical properties of the aqueous dispersion obtained in each Example were measured in the same manner as in Example 1. The composition of the raw materials of the aqueous dispersion in each Example is shown in Table 1. The measurement results of the physical properties of the aqueous dispersion in each Example are shown in Table 1.

[0132] The properties of the aqueous dispersion and coating film obtained in each Example were evaluated in the same manner as in Example 1. The evaluation results of the aqueous dispersion and coating film in each Example are shown in Table 4.

[0133] (Comparative Examples 1 to 2 and Comparative Examples 4 to 7) Except for changing the composition ratio of the raw materials, aqueous dispersions were prepared in the same manner as in Example 1. The physical properties of the aqueous dispersions obtained in each Comparative Example were measured in the same manner as in Example 1. The composition of the raw materials for the aqueous dispersions in each Comparative Example are shown in Tables 2 and 3. The measurement results for the physical properties of the aqueous dispersions in each Comparative Example are shown in Tables 2 and 3. In the columns for physical properties in Tables 2 and 3, "-" indicates that the corresponding physical property was not measured.

[0134] Vinyblan 278 (manufactured by Nissin Chemical Industry Co., Ltd.) shown in Tables 2 and 3 is a vinyl chloride emulsion with a solid content of 43%. The vinyl chloride resin contained in Vinyblan 278 does not have a core-shell structure and contains a surfactant with a molecular weight of 1000 or less as a stabilizer.

[0135] Comparative Example 3 JONCRYL JDX-6500 (manufactured by BASF, active ingredient 30%) and Snowtex S (manufactured by Nissan Chemical Industries, Ltd., active ingredient 30%, particle size 9 nm) were mixed in the ratio shown in Table 2. This resulted in an aqueous dispersion. The solid content of the aqueous dispersion of Comparative Example 3 was measured in the same manner as in Example 1. The measurement results of the solid content are shown in Table 2.

[0136] Comparative Example 8 Snowtex S (Nissan Chemical Industries, active ingredient 30%, particle size 9 nm) and Vinyblan 278 (Nisshin Chemical Industries, Ltd.) were mixed in the ratio shown in Table 3. This resulted in an aqueous dispersion. The solid content of the aqueous dispersion of Comparative Example 8 was measured in the same manner as in Example 1. The measurement results of the solid content are shown in Table 3.

[0137] As described above, in Comparative Examples 3 and 8, vinyl chloride was not included in the raw materials, and the production process of the aqueous dispersion did not include a polymerization process. Therefore, the aqueous dispersions of Comparative Examples 3 and 8 were simply mixtures of raw materials. In Comparative Example 4, vinyl chloride was included in the raw materials, but the vinyl chloride resin could not be polymerized in the production process of the aqueous dispersion. Therefore, in Comparative Example 4, an aqueous dispersion of vinyl chloride resin was not obtained.

[0138] (Evaluation of each comparative example) The properties of the aqueous dispersions and coatings obtained in each Comparative Example were evaluated using the same procedures as in Example 1. The evaluation results of the aqueous dispersions and coatings in each Comparative Example are shown in Tables 5 and 6. In Tables 5 and 6, "-" indicates that the corresponding property was not evaluated.

[0139] The aqueous dispersions of Comparative Examples 1 and 6 had a large degree of cissing, and it was not possible to prepare a coating film using these aqueous dispersions. Therefore, it was not possible to evaluate the coatability, water resistance, alcohol resistance, pencil hardness, and dynamic friction coefficient of the coating film produced by the aqueous dispersions of Comparative Examples 1 and 6.

[0140] As described above, no aqueous dispersion of vinyl chloride resin was obtained in Comparative Example 4. Therefore, for the aqueous dispersion of Comparative Example 4, it was not possible to evaluate the coatability, water resistance, alcohol resistance, pencil hardness, and dynamic friction coefficient of the coating film.

[0141] The coating films prepared using the aqueous dispersions of Comparative Examples 5 and 7 had obvious irregularities on the surfaces of the coating films. Therefore, it was determined that it would be difficult to accurately evaluate the pencil hardness and dynamic friction coefficient of the coating films, and therefore the aqueous dispersions of Comparative Examples 5 and 7 were not evaluated for pencil hardness and dynamic friction coefficient.

[0142] The coating film prepared using the aqueous dispersion of Comparative Example 8 peeled off even when touched with a hand. Therefore, it was determined that it would be difficult to accurately evaluate the pencil hardness and dynamic friction coefficient of the coating film, and therefore the aqueous dispersion of Comparative Example 8 was not evaluated for pencil hardness and dynamic friction coefficient.

[0143] [Table 1]

[0144] [Table 2]

[0145] [Table 3]

[0146] [Table 4]

[0147] [Table 5]

[0148] [Table 6]

[0149] It can be seen from Tables 4 to 6 that compositions (e.g., coating films) having excellent alcohol resistance can be prepared using the aqueous dispersions according to Examples 1 to 4. In particular, the aqueous dispersions according to Examples 1 to 4 provide compositions having excellent water resistance, alcohol resistance, and flexibility.

[0150] For example, when the aqueous dispersion according to the present embodiment is used as an aqueous ink or a raw material for an aqueous ink, an aqueous ink having excellent water resistance, moisture resistance, high gloss, and alcohol resistance is obtained. Also, when the aqueous dispersion according to the present embodiment is used as a raw material for a recording medium, a recording medium having excellent color development, water resistance, moisture resistance, color visibility, and high gloss is obtained. This shows that the aqueous dispersion according to the present embodiment has properties that are particularly suitable for applications such as ink, paint, binder for inorganic material dispersion, receiving layer for recording medium, and treatment agent for fibers.

[0151] Although the present invention has been described above using the embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It is clear to those skilled in the art that various modifications or improvements can be made to the above embodiments. Furthermore, the matters described for a specific embodiment can be applied to other embodiments to the extent that they are not technically inconsistent. Furthermore, each component may have the same features as other components having the same name and different reference numerals. It is clear from the claims that such modified or improved forms may also be included in the technical scope of the present invention.

[0152] It should be noted that the order of execution of each process, such as operations, procedures, steps, and stages, in the devices, systems, programs, and methods shown in the claims, specifications, and drawings is not specifically stated as "before," "prior to," etc., and may be realized in any order unless the output of a previous process is used in a later process. Even if the operational flow in the claims, specifications, and drawings is explained using "first," "next," etc. for convenience, it does not mean that it is essential to perform the process in this order. [Explanation of symbols]

[0153] 100 Recording media 110 Base material 120 Recording Layer 130 Dispersion 132 Dispersion medium 134 Dispersoid 136 Stabilizer 140 Paint 150 paint layer 210 cores 212 Vinyl chloride resin 220 Water-dispersible oligomer

Claims

1. A vinyl chloride polymer, A water-dispersible polymer having a weight average molecular weight of 5,000 or more and 50,000 or less; solid particles having a median diameter of less than 1 μm as measured by a dynamic light scattering method and having hydrophilic functional groups on their surfaces; Including, the vinyl chloride polymer is contained in an amount of 10 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles; the water-dispersed polymer is contained in an amount of 5 parts by mass or more and 40 parts by mass or less relative to a total of 100 parts by mass of the vinyl chloride polymer, the water-dispersed polymer, and the solid particles, the solid particles are contained in an amount of 5 parts by mass or more and less than 50 parts by mass relative to 100 parts by mass in total of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles, 1. An aqueous dispersion comprising:

2. The water-dispersible polymer has at least one of a carboxy group and a urethane group. The aqueous dispersion of claim 1.

3. The water-dispersible polymer includes at least one of a polymer of an ethylenically unsaturated group-containing monomer and a urethane-based polymer. The aqueous dispersion of claim 1.

4. The water-dispersible polymer contains at least one of an acrylic acid ester oligomer, a styrene-acrylic acid ester oligomer, and a polycarbonate-based urethane oligomer. The aqueous dispersion of claim 1.

5. the vinyl chloride polymer and the water-dispersed polymer form a core-shell structure in which the water-dispersed polymer covers the vinyl chloride polymer; The aqueous dispersion of claim 1.

6. the solid particles are bound to the water-dispersible polymer constituting the core-shell structure by intermolecular interactions; The aqueous dispersion according to claim 5.

7. (i) The content of the surfactant having a molecular weight of 1000 or less in the aqueous dispersion is 100 g / m ３ is equal to or less than (ii) the ratio of the mass of the surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride polymer is less than 0.001 mass%; The aqueous dispersion of claim 1.

8. The ratio of the mass of the solid content of the aqueous dispersion to the mass of the aqueous dispersion is 10 mass% or more and 50 mass% or less. The aqueous dispersion of claim 1.

9. The solid particles contain colloidal silica having a median diameter of 6 nm to 100 nm as measured by a dynamic light scattering method. The aqueous dispersion of claim 1.

10. An aqueous dispersion obtained by polymerizing the vinyl chloride monomer in a reaction liquid obtained by mixing a vinyl chloride monomer, a water-dispersed polymer having a weight average molecular weight of 5,000 to 50,000, solid particles having a median diameter of less than 1 μm as measured by a dynamic light scattering method and having hydrophilic functional groups on the surface thereof, and an aqueous solvent, the reaction liquid contains 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer relative to 100 parts by mass in total of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles, the reaction liquid contains the water-dispersed polymer in an amount of 5 parts by mass or more and 40 parts by mass or less relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles, the reaction liquid contains 5 parts by mass or more and less than 50 parts by mass of the solid particles relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersible polymer, and the solid particles, Aqueous dispersion.

11. (i) The concentration of the surfactant having a molecular weight of 1000 or less in the aqueous dispersion is 100 g / m ３ is equal to or less than (ii) the ratio of the mass of the surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride monomer is less than 0.001 mass%; The aqueous dispersion of claim 10.

12. The aqueous dispersion according to any one of claims 1 to 11, Water-based ink.

13. A recording layer comprising a composition derived from the aqueous dispersion according to any one of claims 1 to 11. Recording medium.

14. A substrate; A recording layer disposed on at least one side of the substrate; Equipped with The recording layer is A vinyl chloride polymer, A water-dispersible polymer having a weight average molecular weight of 5,000 or more and 50,000 or less; solid particles having a median diameter of less than 1 μm as measured by a dynamic light scattering method and having hydrophilic functional groups on their surfaces; Including, the recording layer contains the vinyl chloride polymer in an amount of 10 parts by mass or more and less than 70 parts by mass per 100 parts by mass of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles; the recording layer contains the water-dispersible polymer in an amount of 5 parts by mass or more and 40 parts by mass or less relative to 100 parts by mass in total of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles, the recording layer contains the solid particles in an amount of 5 parts by mass or more and less than 50 parts by mass per 100 parts by mass of the vinyl chloride polymer, the water-dispersible polymer, and the solid particles; Recording medium.

15. preparing a reaction liquid by mixing vinyl chloride monomer, a water-dispersed polymer having a weight average molecular weight of 5,000 to 50,000, solid particles having a median diameter of less than 1 μm as measured by a dynamic light scattering method and having hydrophilic functional groups on the surface thereof, and an aqueous solvent; polymerizing the vinyl chloride monomer in the presence of the water-dispersed polymer and the solid particles; having the reaction liquid contains 10 parts by mass or more and less than 70 parts by mass of the vinyl chloride monomer relative to 100 parts by mass in total of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles, the reaction liquid contains the water-dispersed polymer in an amount of 5 parts by mass or more and 40 parts by mass or less relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersed polymer, and the solid particles, the reaction liquid contains 5 parts by mass or more and less than 50 parts by mass of the solid particles relative to a total of 100 parts by mass of the vinyl chloride monomer, the water-dispersible polymer, and the solid particles, A method for producing an aqueous dispersion.

16. The step of polymerizing the vinyl chloride monomer comprises: (i) The concentration of the surfactant having a molecular weight of 1,000 or less in the reaction solution is 100 g / m ３ or (ii) polymerizing the vinyl chloride monomer under the following conditions: (i) a ratio of the mass of a surfactant having a molecular weight of 1000 or less to the mass of the vinyl chloride monomer is less than 0.001% by mass; Including, A method for producing the aqueous dispersion of claim 15.

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