Aqueous dispersions and their uses

Abstract

To provide an aqueous dispersion with good dispersibility. [Solution] Surface free energy is 70 mJ / m 2 It contains particles smaller than 70 mJ / m², a non-fluorinated surfactant, and a non-fluorinated dispersant, wherein the content of the non-fluorinated surfactant is such that the surface free energy is 70 mJ / m². 2 For every 100 parts by mass of particles less than 100 parts by mass, the content of the non-fluorinated dispersant is 0.01 parts by mass or more, and the surface free energy is 70 mJ / m 2 For every 100 parts by mass of particles less than 100 parts by mass, the total content of the nonfluorine-based surfactant and the nonfluorine-based dispersant is such that the surface free energy is 70 mJ / m². 2 An aqueous dispersion containing 25 parts by mass or less per 100 parts by mass of particles smaller than a certain size.

Description

[Technical Field]

[0001] This disclosure relates to aqueous dispersions and their uses. [Background technology]

[0002] Conventionally, fluorine-based surfactants have been used to disperse particles with low surface free energy, such as inorganic pigments and polytetrafluoroethylene (PTFE) particles, in aqueous solvents.

[0003] For example, Patent Document 1 describes a powder dispersion comprising a powder of a first polymer having units based on tetrafluoroethylene and oxygen-containing polar groups, a powder of a second polymer containing units based on fluoroolefin, a dispersant, and a liquid dispersion medium, wherein the ratio of the mass content of the first polymer to the mass content of the second polymer is 0.7 or less.

[0004] Patent Document 2 describes a surfactant that includes a fluorine-containing polymer obtained by copolymerizing a (meth)acrylic monomer containing a perfluoropolyether chain whose repeating unit consists only of "CF2O" with one or more fluorine-free (meth)acrylic monomers. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2020 / 004339 [Patent Document 2] Japanese Patent Application Publication No. 2022-191185 [Overview of the project] [Problems that the invention aims to solve]

[0006] The invention described in Patent Document 1 has problems in that it has a large environmental impact and does not disperse well because it uses a fluorine-based surfactant.

[0007] When a dispersion is prepared using the fluorinated surfactant described in Patent Document 2, there are problems in that it has a high environmental impact and does not disperse sufficiently because a fluorinated surfactant is used.

[0008] Due to concerns about bioaccumulation in the body and environmental persistence, fluorinated surfactants are subject to PFAS regulations, and there is a strong demand for alternatives.

[0009] On the other hand, dispersions prepared using surfactants that do not contain fluorine (non-fluorinated surfactants) required a large amount of the surfactant to be added in order to disperse the particles, and also had the problem of poor dispersibility.

[0010] This disclosure has been made in view of the above and aims to provide an aqueous dispersion having good dispersibility. [Means for solving the problem]

[0011] The inventors conducted extensive research to achieve the above objective, and as a result, found that the surface free energy is 70 mJ / m 2 We have found that the above problem can be solved by using an aqueous dispersion containing particles smaller than 100, a non-fluorinated surfactant, and a non-fluorinated dispersant. This disclosure is the result of further research by the inventors.

[0012] This disclosure includes, for example, the following subjects: Surface free energy is 70 mJ / m 2 It contains particles smaller than a certain size, a non-fluorinated surfactant, and a non-fluorinated dispersant. The content of the non-fluorinated surfactant is such that the surface free energy is 70 mJ / m 2 For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The content of the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m 2 For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The total content of the non-fluorinated surfactant and the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m 2 An aqueous dispersion containing 25 parts by mass or less per 100 parts by mass of particles smaller than a certain size. [Effects of the Invention]

[0013] The present disclosure provides an aqueous dispersion with good dispersibility. Because of these excellent properties, the aqueous dispersion of the present disclosure can be suitably used in a wide range of applications, including coatings, paints, lubricating films, and batteries. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a photograph showing the dispersion state of the aqueous dispersion (solid content concentration of PTFE particles: 50% by mass) prepared in Example 1. [Figure 2] Figure 2 is a photograph of the aqueous dispersion prepared in Example 1, taken with a scanning electron microscope (SEM) at approximately 10,000x magnification. [Figure 3] Figure 3 shows images taken with a scanning electron microscope (SEM) at approximately 5000x magnification of the state of the PTFE particles used in each example and comparative example before dispersion. [Modes for carrying out the invention]

[0015] Preferred embodiments of this disclosure are described in detail below. The descriptions of constituent elements below may be based on representative embodiments and specific examples, but this disclosure is not limited to such embodiments.

[0016] In this disclosure, the expressions “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consists of,” and “consistes of only.”

[0017] In the numerical ranges described in stages in this disclosure, the upper or lower limit of one stage of the numerical range can be arbitrarily combined with the upper or lower limit of another stage of the numerical range. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with values ​​shown in the examples or values ​​that can be uniquely derived from the examples.

[0018] In this disclosure, “A and / or B” means “either A or B” or “both A and B,” and more specifically, “A,” “B,” or “A and B.”

[0019] In this disclosure, "n-" means "normal," "sec-" means "secondary," and "tert-" means "tertiary."

[0020] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0021] In this disclosure, room temperature means a temperature within the range of 20°C to 25°C.

[0022] In this disclosure, “monomer backbone” means a carbon chain containing polymerizable double bonds (carbon-carbon double bonds). In this disclosure, “monomer side chain” means a chain attached to the monomer backbone that is shorter in length than the backbone.

[0023] In this disclosure, the content of component unit (A) derived from monomer (a) having a phenyl group in all component units of the copolymer can be considered to be equal to the amount of monomer (a) having a phenyl group used relative to the total amount of monomer used in the production of the copolymer.

[0024] In this disclosure, the content of a component unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group in all component units of the copolymer can be considered to be equal to the amount of monomer (b) having a hydroxyl group or a phosphate group used relative to the total amount of monomer used in the production of the copolymer.

[0025] In this disclosure, examples of linear or branched alkyl groups having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, and the like.

[0026] In this disclosure, examples of linear or branched alkylene groups having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, cyclopentylene group, n-hexylene group, n-heptylene group, n-octylene group, n-nonylene group, n-decylene group, and the like.

[0027] In this disclosure, a linear or branched oxyalkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) is a group represented by -AO-, where A is a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0028] In the present disclosure, an oxyalkylene group having 1 to 3 (1, 2 or 3) carbon atoms is -CH2-O-, -CH2-CH2-O-, -CH2-CH2-CH2-O-, or -CH2-CH(CH3)-O-.

[0029] 1.Aqueous dispersion The aqueous dispersion of the present disclosure has the following configurations (I), (II), (III) and (IV). (I) Particles having a surface free energy of less than 70 mJ / m 2 , a non-fluorinated surfactant, and a non-fluorinated dispersant. (II) The content of the non-fluorinated surfactant is, for particles having a surface free energy of less than 70 mJ / m 2 , 0.01 part by mass or more based on 100 parts by mass of the particles. (III) The content of the non-fluorinated dispersant is, for particles having a surface free energy of less than 70 mJ / m 2 , 0.01 part by mass or more based on 100 parts by mass of the particles. (IV) The total content of the non-fluorinated surfactant and the non-fluorinated dispersant is, for particles having a surface free energy of less than 70 mJ / m 2 , 25 parts by mass or less based on 100 parts by mass of the particles.

[0030] By having the above-described configurations (I), (II), (III) and (IV), the aqueous dispersion of the present disclosure provides good dispersibility of particles having a surface free energy of less than 70 mJ / m 2 in an aqueous solvent. In the present disclosure, the mechanism by which such an effect is obtained is speculated, for example, as follows, but the technical scope of the present disclosure is not limited to the following mechanism.

[0031] The use of a non-fluorinated surfactant mainly reduces the surface tension of the aqueous solvent, and as a result, the surface free energy is less than 70 mJ / m 2 It is considered that the wettability of the particles to an aqueous solvent is improved. By using a non-fluorinated dispersant, the non-fluorinated dispersant mainly acts on particles having a surface free energy of less than 70 mJ / m 2It adheres to the surface of particles smaller than 70 mJ / m², and due to steric repulsion of the non-fluorinated dispersant, etc., the surface free energy is 70 mJ / m². 2 It is believed that particles smaller than 70 mJ / m² can be dispersed and their dispersion state maintained. By using a non-fluorinated surfactant and a non-fluorinated dispersant in combination, the surface free energy is 70 mJ / m², compared to using either one alone. 2 It is believed that particles smaller than a certain size can be dispersed more efficiently in an aqueous solvent, and that the amount of both non-fluorinated surfactants and non-fluorinated dispersants used can be reduced.

[0032] As one embodiment of the present disclosure, the aqueous dispersion of the present disclosure has a surface free energy of 70 mJ / m 2 The lower limit of the content of non-fluorinated surfactant per 100 parts by mass of particles less than 70 mJ / m² can be 0.01 parts by mass, 0.05 parts by mass, 0.1 parts by mass, 0.5 parts by mass, 1.0 parts by mass, 1.5 parts by mass, 2.0 parts by mass, 2.5 parts by mass, and 3.0 parts by mass, with a surface free energy of 70 mJ / m². 2 The upper limit for the content of non-fluorinated surfactants per 100 parts by mass of particles less than 1 can be 24.99 parts by mass, 24 parts by mass, 22 parts by mass, 20 parts by mass, 18 parts by mass, 16 parts by mass, and 15 parts by mass, and these lower and upper limits can be combined arbitrarily.

[0033] As one embodiment of the present disclosure, the aqueous dispersion of the present disclosure has a surface free energy of 70 mJ / m 2 The lower limit of the content of non-fluorinated dispersant per 100 parts by mass of particles less than 100 parts by mass can be 0.01 parts by mass, 0.05 parts by mass, 0.1 parts by mass, 0.5 parts by mass, and 1.0 parts by mass, and the surface free energy is 70 mJ / m 2 The upper limit for the content of a non-fluorinated dispersant per 100 parts by mass of particles less than 1 can be 24.99 parts by mass, 24 parts by mass, 22 parts by mass, 20 parts by mass, 18 parts by mass, 16 parts by mass, 14 parts by mass, 12 parts by mass, and 10 parts by mass, and these lower and upper limits can be combined arbitrarily.

[0034] As one embodiment of the present disclosure, the aqueous dispersion of the present disclosure has a surface free energy of 70 mJ / m2 The total content of non-fluorinated surfactant and non-fluorinated dispersant per 100 parts by mass of particles smaller than 100 parts by mass is preferably 24 parts by mass or less, more preferably 22 parts by mass or less, even more preferably 20 parts by mass or less, and still more preferably 18 parts by mass or less.

[0035] In one embodiment of this disclosure, the surface free energy is 70 mJ / m 2 For particles with a surface free energy of less than 50 mJ / m², the surface free energy is preferably 50 mJ / m². 2 More preferably, 45 mJ / m 2 More preferably, 40 mJ / m 2 More preferably, 36 J / m 2 The following applies:

[0036] In one embodiment of this disclosure, the surface free energy is 70 mJ / m 2 Particles smaller than the specified size are preferable because they exhibit better dispersibility. Polytetrafluoroethylene particles (surface free energy = 18 mJ / m) 2 ), Hydrocarbon particles (surface free energy = 22 mJ / m) 2 ), Polyethylene particles (surface free energy = 31 mJ / m) 2 ), Polystyrene particles (surface free energy = 33 mJ / m 2 ), Polyvinylidene fluoride particles (surface free energy = 33 mJ / m) 2 ), Polyvinyl alcohol particles (surface free energy = 37 mJ / m 2 ), Polyvinyl chloride particles (surface free energy = 39 mJ / m 2 ), Polyvinyldenium chloride particles (surface free energy = 40 mJ / m) 2 ), Polyethylene terephthalate particles (surface free energy = 43 mJ / m) 2 ), Nylon particles (surface free energy = 46 mJ / m2 ), Zinc oxide particles (surface free energy = 30.6~35.8 mJ / m 2 ) and Carbon nanotube granules (surface free energy = 40 mJ / m 2 More than 70mJ / m 2 It is at least one particle selected from the group consisting of (less than)

[0037] In one embodiment of this disclosure, the surface free energy is 70 mJ / m 2 Particles smaller than a certain size are more preferably polytetrafluoroethylene particles or carbon nanotube granules, as they exhibit even better dispersibility.

[0038] As one embodiment of this disclosure, the surface free energy in the total solid content of the aqueous dispersion is set to 70 mJ / m², which improves dispersibility. 2 The content of particles smaller than 60% by mass is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

[0039] In this disclosure, the surface free energy is 70 mJ / m 2 One method for measuring the surface free energy of particles less than mJ / m is the OWRK (Owens-Wendt-Rabel-Kaelble) method. Specifically, based on the OWRK (Owens-Wendt-Rabel-Kaelble) method, water and diiodomethane, whose surface free energies are known, are used. Water is dropped onto the surface of the compacted particle and the contact angle of the water is measured. Then, diiodomethane is dropped onto the surface of the compacted particle and the contact angle of the diiodomethane is measured. This allows the surface free energy of the particle (mJ / m) to be determined. 2 Calculate ).

[0040] In this disclosure, a non-fluorinated surfactant means a surfactant that does not contain any fluorine atoms in its molecule.

[0041] In this disclosure, a non-fluorinated dispersant means a dispersant that does not contain any fluorine atoms in its molecule.

[0042] As one embodiment of this disclosure, non-fluorinated surfactants have better dispersibility, Preferably, it is at least one selected from the group consisting of nonfluorinated nonionic surfactants, nonfluorinated anionic surfactants, nonfluorinated cationic surfactants, and nonfluorinated amphoteric surfactants. More preferably, a non-fluorinated nonionic surfactant and / or a non-fluorinated anionic surfactant, More preferably, it is a non-fluorinated nonionic surfactant or a non-fluorinated anionic surfactant.

[0043] As one embodiment of the present disclosure, examples of nonfluorinated nonionic surfactants include polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene phenyl ethers, polyoxypropylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyalkylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, and the like. These can be used individually or in combination of two or more.

[0044] Examples of polyoxyethylene alkyl ethers include polyoxyethylene dodecyl ether (polyoxyethylene lauryl ether), polyoxyalkylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyalkylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene behenyl ether, polyoxyethylene-2-ethylhexyl ether, and polyoxyethylene isodecyl ether. These can be used individually or in combination of two or more.

[0045] Examples of polyoxypropylene alkyl ethers include polyoxypropylene cetyl ether, polyoxypropylene isocetyl ether, polyoxypropylene stearyl ether, and polyoxypropylene oleyl ether, which can be used individually or in combination of two or more.

[0046] Examples of polyoxyethylene phenyl ethers include polyoxyethylene octylphenyl ether, polyoxyethylene oleylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene styrene-derived phenyl ether, polyoxyethylene disstyrene-derived phenyl ether, and polyoxyethylene tripenzylphenyl ether. These can be used individually or in combination of two or more types.

[0047] Examples of polyoxyethylene alkyl esters include polyoxyethylene laurate, polyoxyethylene palmitate, polyoxyethylene stearate, and polyoxyethylene oleate, which can be used individually or in combination of two or more.

[0048] Examples of polyoxyalkylene fatty acid esters include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol distearate; and polyoxypropylene fatty acid esters such as polypropylene glycol monostearate and polypropylene glycol distearate. These can be used individually or in combination of two or more.

[0049] In one embodiment of this disclosure, a polyoxyethylene alkyl ether is preferred as the non-fluorinated nonionic surfactant because it provides even better dispersibility.

[0050] As one embodiment of the present disclosure, examples of non-fluorinated anionic surfactants include alkyl sulfosuccinates, alkyl sulfate salts, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphate salts, polyoxyethylene alkyl ether sulfate salts, polyoxyethylene polycyclic phenyl ether sulfate salts, polyoxyethylene distyrenated phenyl ether sulfate salts, fatty acid salts, polyoxyethylene alkylphenyl ether sulfate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene aryl ether phosphate salts, and polyoxyethylene aryl ether phosphate salts, which can be used individually or in combination of two or more. In the present disclosure, when a non-fluorinated anionic surfactant forms a salt, the salt may be a metal salt such as a sodium salt, or a non-metal salt such as an ammonium salt or an amine salt.

[0051] As one embodiment of this disclosure, polyoxyethylene alkyl ether phosphate is preferred as the non-fluorinated anionic surfactant because it provides even better dispersibility.

[0052] As one embodiment of the present disclosure, a non-fluorinated cationic surfactant is, for example, Alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, oleyltrimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, coconut oil alkyltrimethylammonium chloride, stearyltrimethylammonium bromide, coconut oil alkyltrimethylammonium bromide, cetyltrimethylammonium methosulfate, oleyldimethylethylammonium ethosulfate, dioctyldimethylammonium chloride, dilauryldimethylammonium chloride, distearyldimethylammonium chloride, octadecyldiethylmethylammonium sulfate, and other alkyl quaternary ammonium salts; (Polyoxyethylene) laurylaminoether lactate, stearylaminoether lactate, di(polyoxyethylene) laurylmethylaminoetherdimethylphosphate, and other (polyoxyalkylene) alkylaminoether salts; Acylamide alkyl quaternary ammonium salts such as N-(2-hydroxyethyl)-N,N-dimethyl-N-stearoylamidopropylammonium nitrate, lanolin fatty acid amidopropylethyldimethylammonium ethosulfate, and lauroylamidoethylmethyldiethylammonium methosulfate; Alkylisoquinolinium salts such as laurylisoquinolinium chloride; Benzalkonium salts such as lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride; Benzethonium salts such as benzyldimethyl{2-[2-(p-1,1,3,3-tetramethylbutylphenoxy)ethoxy]ethyl}ammonium chloride; Pyridinium salts such as cetylpyridinium chloride; Examples include imidazolinium salts such as oleyl hydroxyethyl imidazolinium ethosulfate and lauryl hydroxyethyl imidazolinium ethosulfate, which can be used individually or in combination of two or more.

[0053] As one embodiment of the present disclosure, a nonfluorinated amphoteric surfactant is, for example, Imidazolin-type amphoteric surfactants such as 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydrooxide-1-carboxyethyloxy disodium salt; Betaine-type amphoteric surfactants such as fatty acid amidopropyl betaine, fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, alkyl hydroxysulfobetaine, alkyl carboxybetaine, alkyl sulfobetaine, alkylamidopropyl hydroxysulfobetaine, alkyl hydroxyphosphobetaine, and alkylimidazolinium betaine; Amino acid-type amphoteric surfactants such as sodium β-laurylaminopropionate and alkylaminocarboxylate salts; Examples include amine oxide-type amphoteric surfactants such as lauryldimethylamine oxide and alkylamine oxide, which can be used individually or in combination of two or more.

[0054] In one embodiment of the present disclosure, it is preferable that the nonfluorinated dispersant comprises a copolymer, the copolymer containing a constituent unit (A) derived from a monomer (a) having a phenyl group.

[0055] In this disclosure, "monomer (a) having a phenyl group" will also be referred to as "monomer (a)".

[0056] In one embodiment of the present disclosure, the non-fluorinated dispersant of the present disclosure preferably has a mass-average molecular weight of 500 to 20000.

[0057] In one embodiment of the present disclosure, the non-fluorinated dispersant of the present disclosure preferably has a number-average molecular weight of 500 to 20,000.

[0058] In one embodiment of the present disclosure, the copolymer content is typically more than 50% by mass, preferably 75% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 99% by mass or more, even more preferably 99.5% by mass or more, and particularly preferably 99.9% by mass or more, when the total mass of the non-fluorinated dispersant is taken as 100% by mass.

[0059] In another embodiment of the present disclosure, it is most preferable that the non-fluorinated dispersant of the present disclosure consists solely of a copolymer. However, the inclusion of unavoidable impurities (for example, trace amounts of solvent remaining after purification during the manufacturing process of the non-fluorinated dispersant, trace amounts of residual monomer, etc.) is permissible.

[0060] In one embodiment of the present disclosure, monomer (a) is preferably monomer (a) having a phenyl group having one, two, three, four, or five substituents.

[0061] In one embodiment of the present disclosure, monomer (a) is preferably a monomer (a) having a phenyl group having 1, 2, 3, 4, or 5 hydroxyl groups, more preferably a monomer (a) having a phenyl group having 1, 2, 3, or 4 hydroxyl groups, even more preferably a monomer (a) having a phenyl group having 1, 2, or 3 hydroxyl groups, and still more preferably a monomer (a) having a phenyl group having 2 or 3 hydroxyl groups.

[0062] In one embodiment of the present disclosure, the monomer (a) having a phenyl group is preferably a monomer (a) having a catechol group or a galloyl group, more preferably a monomer (a) having a catechol group.

[0063] In one embodiment of the present disclosure, monomer (a) typically does not have a phosphate group.

[0064] In one embodiment of the present disclosure, the monomer (a) having a phenyl group is preferably a monomer represented by the following formula (1). [ka] (In the formula, R 1 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R 2 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R 3 -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O- represent a single bond, -O-, -CH(OH)-, -OC(=O)O-, or -OC(=O)O-. R 4 , R 5 , R 6 , R 7 and R 8 Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R 4 , R 5 , R 6 , R 7 and R 8 (Except when all atoms are hydrogen atoms.)

[0065] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 1 It is preferable that this is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0066] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 1 It is more preferable that this is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).

[0067] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 1It is more preferable that the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0068] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 1 It is particularly preferable that this is a hydrogen atom or a methyl group.

[0069] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 1 It is most preferable that it is a methyl group.

[0070] In formula (1) of this disclosure, R 2 A single bond is R 2 (i.e., R 2 X and R adjacent to each other 3 This means that (and are directly joined together).

[0071] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 2 This is preferably a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), which may have substituents.

[0072] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 2 This is more preferably an alkylene group having 1 to 3 carbon atoms (1, 2, or 3), which may have substituents.

[0073] As one embodiment of this disclosure, R in formula (1) of this disclosure 2 Examples of substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, hydroxyl groups, amino groups, ester groups, carboxyl groups, epoxy groups, isocyanate groups, phenyl groups, etc., and these can be used individually or in combination of two or more. In this disclosure, R of formula (1) 2 Except when the substituent in is a phosphate group.

[0074] As one embodiment of this disclosure, R in formula (1) of this disclosure 2In this, the number of substituents is usually one to four, preferably one or two, and more preferably one.

[0075] As one embodiment of this disclosure, R in formula (1) of this disclosure 2 In this, the substituent is preferably one to four hydroxyl groups, more preferably one or two hydroxyl groups, and even more preferably one hydroxyl group.

[0076] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 3 Preferably, it is a single bond or -OC(=O)-.

[0077] As one embodiment of the present disclosure, in formula (1) of the present disclosure, R 3 A single bond is R 3 (i.e., R 3 Adjacent to R 2 This means that the phenyl group with a substituent is directly bonded to it.

[0078] A preferred embodiment of the present disclosure is, in formula (1) of the present disclosure, R 4 and R 8 Both are hydrogen atoms, R 5 , R 6 and R 7 Both are hydroxyl groups; or R 4 and R 8 Both are hydrogen atoms, R 6 is a hydroxyl group, R 5 and R 7 One of them is a hydroxyl group, and the other is a hydrogen atom.

[0079] A more preferred embodiment of the present disclosure is, in formula (1) of the present disclosure, R 1 However, if X is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and X is -C(=O)NH- or -C(=O)O-, then R2 is a linear or branched alkylene group having 1 to 6 (1, 2, 3, 4, 5 or 6) carbon atoms which may have a substituent, and R 3 is a single bond, and R 4 and R 8 are both hydrogen atoms, R 6 is a hydroxy group, and R 5 and R 7 one is a hydroxy group and the other is a hydrogen atom; or when X is -C(=O)O-, R 2 is a linear or branched alkylene group having 1 to 6 (1, 2, 3, 4, 5 or 6) carbon atoms which may have a substituent (preferably a hydroxy group), and R 3 is -OC(=O)-, and R 4 and R 8 are both hydrogen atoms, R 6 is a hydroxy group, and R 5 and R 7 one is a hydroxy group and the other is a hydrogen atom.

[0080] As one embodiment of the present disclosure, when X is -C(=O)NH-, the monomer (a) represented by formula (1) of the present disclosure is preferably N-[2-(3,4-dihydroxyphenyl)methyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)ethyl] (meth)acrylamide [also known as dopamine methacrylamide (DMA)], N-[2-(3,4-dihydroxyphenyl)propyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)butyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)pentyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)hexyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)heptyl] (meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)octyl](meth)acrylamide, N-[2-(3,4-dihydroxyphenyl)nonyl](meth)acrylamide and N-[2-(3,4-dihydroxyphenyl)decyl](meth)acrylamide It is at least one selected from the group consisting of the following:

[0081] In one embodiment of the present disclosure, the monomer (a) represented by formula (1) of the present disclosure is preferably such that X is -C(=O)O- when X is -C(=O)O- N-[2-(3,4-dihydroxyphenyl)methyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)ethyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)propyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)butyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)pentyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)hexyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)heptyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)octyl](meth)acrylate, N-[2-(3,4-dihydroxyphenyl)nonyl](meth)acrylate N-[2-(3,4-dihydroxyphenyl)decyl](meth)acrylate and 3,4,5-Trihydroxybenzoic acid [2-hydroxy-3-(methacrylroyloxy)propyl]ester It is at least one selected from the group consisting of the following:

[0082] In one embodiment of the present disclosure, the nonfluorinated dispersant preferably comprises a copolymer, wherein the copolymer contains a constituent unit (A) derived from a monomer (a) having a phenyl group and a constituent unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group.

[0083] In this disclosure, "monomer (b) having a hydroxyl group or a phosphate group" is also referred to as "monomer (b)".

[0084] In monomer (b) of this disclosure, the hydroxyl group does not typically include the hydroxyl group that is present in a carboxyl group (-COOH).

[0085] In one embodiment of the present disclosure, monomer (b) of the present disclosure preferably has one or two hydroxyl groups and preferably one phosphate group.

[0086] In one embodiment of the present disclosure, monomer (b) of the present disclosure typically does not have a phenyl group.

[0087] In one embodiment of the present disclosure, monomer(b) of the present disclosure preferably has a hydroxyl group or a phosphate group at the end of its side chain. In the present disclosure, “end of side chain” means the hydroxyl group or phosphate group furthest from the main chain of monomer(b).

[0088] As one embodiment of the present disclosure, monomer (b) of the present disclosure is Preferably, the side chain has one or two hydroxyl groups or one phosphate group at its terminus, more preferably, the side chain has one hydroxyl group or one phosphate group at its terminus. More preferably, the side chain has one hydroxyl group at its terminal end.

[0089] In one embodiment of the present disclosure, monomer (b) having a hydroxyl group or a phosphate group is preferably a monomer represented by the following formula (2). [ka] (In the formula, R 9 This represents a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20). R 10 This represents a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) which may have substituents. n represents a number between 1 and 20 on average. R 10 However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), which may have substituents, R 11 This indicates a hydroxyl group or a phosphate group. R 10 However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), which may have substituents, R 11 (This represents a hydrogen atom or a phosphate group.)

[0090] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 9 It is preferable that this is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).

[0091] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 9 It is more preferable that this is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).

[0092] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 9 It is more preferable that the group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0093] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 9 It is particularly preferable that this is a hydrogen atom or a methyl group.

[0094] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 9 It is most preferable that it be a hydrogen atom.

[0095] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 10 Preferably, this is a linear or branched alkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6) which may have substituents, or a linear or branched oxyalkylene group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6) which may have substituents.

[0096] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 10 It is more preferable that this is an alkylene group having 1 to 3 carbon atoms (1, 2, or 3) which may have substituents, or an oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3) which may have substituents.

[0097] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 10 It is more preferable that the group is an alkylene group having 1 to 3 carbon atoms (1, 2, or 3), or an oxyalkylene group having 1 to 3 carbon atoms (1, 2, or 3).

[0098] As one embodiment of the present disclosure, in formula (2) of the present disclosure, R 10 It is particularly preferable that the compound is -CH2-CH2-O-.

[0099] In one embodiment of this disclosure, in formula (2) of this disclosure, n is the number of repetitions, and represents a number between 1 and 20 on average. The value of n can be measured by nuclear magnetic resonance (NMR) analysis. Specifically, the value of n can be calculated by measuring the integral value of 3 ppm to 4 ppm.

[0100] In one embodiment of the present disclosure, in formula (2) of the present disclosure, the upper limit of n can take values ​​of 19, 18, 17, 16, 15, 14, 13, 12, 11 and 10, and the lower limit of n can take values ​​of 1.5, 2, 2.5, 3, 3.5, 4 and 4.5, and these upper and lower limits can be combined in any way.

[0101] In one embodiment of the present disclosure, in formula (2) of the present disclosure, n preferably represents a number between 2 and 18 on average, more preferably a number between 2.5 and 16 on average, even more preferably a number between 3 and 14 on average, even more preferably a number between 3.5 and 12 on average, and particularly preferably a number between 4 and 11 on average.

[0102] As one embodiment of this disclosure, R in formula (2) of this disclosure 10 In this disclosure, the substituent is not particularly limited as long as it is not a hydrogen atom, and examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, an amino group, an ester group, a carboxyl group, an epoxy group, a phosphoric acid group, an isocyanate group, etc., and these substituents can be used individually or in combination of two or more. In this disclosure, R of formula (2) 10 Except when the substituent in is a phenyl group.

[0103] As one embodiment of this disclosure, R in formula (2) of this disclosure 10 In this, the number of substituents is usually one to four, preferably one or two, and more preferably one.

[0104] As one embodiment of this disclosure, R in formula (2) of this disclosure 10 In this, the substituent is preferably one to four hydroxyl groups, more preferably one or two hydroxyl groups, and even more preferably one hydroxyl group.

[0105] As one embodiment of the present disclosure, monomer (b) represented by formula (2) of the present disclosure is Preferably, at least one selected from the group consisting of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-methchloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, glycerin monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. More preferably, at least one selected from the group consisting of 2-methachloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, and polypropylene glycol monomethacrylate. More preferably, at least one selected from the group consisting of 2-methachloroyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, polyethylene glycol monoacrylate, and polyethylene glycol monomethacrylate, particularly preferably 2-acryloyloxyethyl acid phosphate and / or polyethylene glycol monoacrylate. Most preferably polyethylene glycol monoacrylate, That is the case.

[0106] As one embodiment of the present disclosure, commercially available monomers (b) represented by formula (2) of the present disclosure include: NOF Corporation's "Bremmer AE-200", "Bremmer AE-400", "Bremmer GLM", "Bremmer GLM-EX", "Bremmer GLM-R", "Bremmer E", "Bremmer PE-90", "Bremmer PE-200", "Bremmer PE-350", "Bremmer AP-200", "Bremmer AP-400", "Bremmer AP-550", "Bremmer AP-800", "Bremmer AP-400D", "Bremmer AP-1000D", "Bremmer P", "Bremmer PP-1000", "Bremmer PP-500", and "Bremmer PP-800"; Kyoeisha Chemical Co., Ltd.'s "Light Acrylate P-1A(N)" and "Light Ester P-1M"; and Hannong Chemicals' "KOREMUL EA-051", "KOREMUL EA-101", "KOREMUL EM-051", and "KOREMUL Examples include "EM-051" and "KOREMUL EMF-063," and these commercially available products can be used individually or in combination of two or more types.

[0107] In one embodiment of the present disclosure, when the total of constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b) is 100 mol%, the content of constituent units (A) derived from monomer (a) is preferably 0.1 mol% to 20 mol%, more preferably 0.3 mol% to 10 mol%, even more preferably 0.5 mol% to 5 mol%, and still more preferably 0.8 mol% to 3 mol%, from the viewpoint of the copolymer having good hydrophilicity.

[0108] In one embodiment of the present disclosure, the copolymer of the present disclosure is preferably water-soluble. In the present disclosure, a water-soluble copolymer means, for example, a copolymer that obtains a "○" rating (transparent and completely dissolved) in the following solubility evaluation method. <Method for evaluating solubility> First, 8g of deionized water and 0.08g of copolymer are added to a glass container, and then the mixture is stirred at room temperature for 30 seconds using a vortex mixer ("Mixer N-61" manufactured by Nisshin Rika Co., Ltd.). After stirring, the mixture is visually inspected and the solubility is evaluated according to the following evaluation criteria. (Evaluation Criteria) ○: Transparent and completely dissolved △: Cloudy and partially dissolved ×: Does not dissolve

[0109] In one embodiment of the present disclosure, the arrangement of constituent units (A) derived from monomer (a) and the arrangement of constituent units (B) derived from monomer (b) may be random, block, graft, or gradient, respectively.

[0110] In one embodiment of the present disclosure, the copolymer may include, for example, a structural unit derived from a chain transfer agent, a structural unit derived from a polymerization initiator, and other structural units other than the structural unit (A) derived from monomer (a) and the structural unit (B) derived from monomer (b).

[0111] As one embodiment of the present disclosure, when the total mass of the copolymer of the present disclosure is 100% by mass, the total content of constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b) is preferably in the order of more than 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, 91% by mass or more, 92% by mass or more, 93% by mass or more, 94% by mass or more, 95% by mass or more, and 96% by mass or more.

[0112] In another embodiment of the present disclosure, it is particularly preferable that the copolymer of the present disclosure consists only of constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b). However, even if the copolymer consists only of constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b), the inclusion of unavoidable impurities in the constituent units (A) derived from monomer (a) and constituent units (B) derived from monomer (b) (for example, trace amounts of solvent remaining after purification during the copolymer manufacturing process) is permissible.

[0113] In one embodiment of this disclosure, the surface free energy is 70 mJ / m 2 The total content ratio of particles smaller than 50%, non-fluorinated surfactants, and non-fluorinated dispersants is preferably in the following order, when the total mass of the aqueous dispersion is taken as 100% by mass: over 50%, 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 92.5% or more by mass, 95% or more by mass, 97.5% or more by mass, 99% or more by mass, 99.5% or more by mass, 99.7% or more by mass, and 99.9% or more by mass, in that order.

[0114] In one embodiment of this disclosure, the surface free energy in the aqueous dispersion of this disclosure is 70 mJ / m². 2 The dispersion stability of particles smaller than a certain size can be evaluated, for example, by the evaluation methods listed below. <Method A for evaluating dispersion stability> The aqueous dispersion is stored at room temperature and humidity of 20-40% for 5 days. The thickness of the settled layer is measured, and if the measured thickness of the settled layer is within the appropriate range, the surface free energy in the aqueous dispersion is 70 mJ / m². 2 The dispersion stability of particles smaller than a certain size can be evaluated as good. <Method B for evaluating dispersion stability> Using the centrifugal sedimentation type dispersion stability particle size distribution device LUMiSizer (manufactured by LUM), the interfacial migration velocity (surface free energy of 70 mJ / m) of an aqueous dispersion was measured. 2 Measure the sedimentation velocity of particles less than 70 mJ / m³, and if the measured interfacial migration velocity is within an appropriate range, the surface free energy in the aqueous dispersion is 70 mJ / m³. 2 The dispersion stability of particles smaller than a certain size can be evaluated as good. <Method C for evaluating dispersion stability> For aqueous dispersions before and after standing, the relaxation times before and after standing are measured using a pulsed nuclear magnetic resonance (pulsed NMR) spectrometer. From these two measured relaxation times, the Rsp value is calculated. If the calculated Rsp value is within an appropriate range, the surface free energy of the aqueous dispersion is 70 mJ / m². 2The dispersion stability of particles smaller than a certain size can be evaluated as good. As a pulsed NMR spectrometer, for example, the "ACORN AREA® Nuclear Magnetic Resonance Dimension Analyzer" manufactured by CORDOUAN Technologies can be used. <Method for evaluating dispersion stability D> Using a rheometer, the viscosity properties of the aqueous dispersion are measured, and if the measured viscosity properties are within an appropriate range, the surface free energy in the aqueous dispersion is 70 mJ / m³. 2 The dispersion stability of particles smaller than a certain size can be evaluated as good. As a rheometer, for example, modular compact rheometers such as the "MCR 102e," "MCR 302e," and "MCR 502e Power" manufactured by Anton Paar GmbH can be used.

[0115] In one embodiment of the present disclosure, the aqueous dispersion of the present disclosure typically has a surface free energy of 70 mJ / m². 2 It contains particles smaller than 70 mJ / m², a non-fluorinated surfactant, a non-fluorinated dispersant, and an aqueous solvent. In this embodiment, the surface free energy is 70 mJ / m². 2 The total content ratio of particles smaller than 50% by mass, non-fluorinated surfactant, non-fluorinated dispersant, and aqueous solvent is preferably in the following order, when the total mass of the aqueous dispersion is taken as 100% by mass: over 50% by mass, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 92.5% by mass or more, 95% by mass or more, 97.5% by mass or more, 99% by mass or more, 99.5% by mass or more, 99.7% by mass or more, 99.9% by mass or more, and 99.99% by mass, when the total mass of the aqueous dispersion is taken as 100% by mass.

[0116] In one embodiment of the present disclosure, the aqueous dispersion of the present disclosure comprises a nonfluorinated surfactant and a nonfluorinated dispersant with a surface free energy of 70 mJ / m². 2 Preferably, the solution contains composite particles attached to the surface of particles smaller than 1, and an aqueous solvent, wherein the composite particles are dispersed in the aqueous solvent.

[0117] In another embodiment of the present disclosure, the aqueous dispersion of the present disclosure has a surface free energy of 70 mJ / m². 2Preferably, the solution contains particles formed by compounding particles smaller than a certain size, a non-fluorinated surfactant, and a non-fluorinated dispersant, and an aqueous solvent, wherein the compounded particles are dispersed in the aqueous solvent.

[0118] In this disclosure, the aqueous solvent can be water, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent. Examples of water include natural water, purified water, distilled water, ion-exchanged water, and pure water.

[0119] In this disclosure, examples of water-soluble organic solvents include alcohol compounds, ketone compounds, ether compounds, amide compounds, sulfoxide compounds, ester compounds, glycol compounds, etc., which can be used individually or in combination of two or more.

[0120] Examples of alcohol compounds in this disclosure include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc., which can be used individually or in combination of two or more.

[0121] Examples of ketone compounds in this disclosure include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, and the like, which can be used individually or in combination of two or more.

[0122] Examples of ether compounds in this disclosure include diethyl ether, tetrahydrofuran (THF), and dioxane, which can be used individually or in combination of two or more.

[0123] Examples of amide compounds in this disclosure include N,N-dimethylformamide (DMF), N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N-methylcaprolactam, which can be used individually or in combination of two or more.

[0124] Examples of sulfoxide compounds in this disclosure include dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, and thiophene, which can be used individually or in combination of two or more.

[0125] Examples of ester compounds in this disclosure include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, and ethyl lactate, which can be used individually or in combination of two or more.

[0126] Examples of glycol compounds in this disclosure include ethylene glycol, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and propylene glycol methyl ether acetate, which can be used individually or in combination of two or more.

[0127] The aqueous dispersion disclosed herein has a surface free energy of 70 mJ / m². 2 When the solid content concentration of particles smaller than 30% by mass or 50% by mass is set, the viscosity is measured by the following viscosity measurement method, at a shear rate of 0.25 s. -1The coefficient of variation of viscosity in the following solution, expressed by the following formula, is preferably less than 28%, more preferably 25% or less, even more preferably 20% or less, and particularly preferably 15% or less. The coefficient of variation of viscosity in this disclosure is determined when the surface free energy of the aqueous dispersion in this disclosure is 70 mJ / m³. 2 If the solid content concentration of particles smaller than 50% by mass is 50% or more, the viscosity is measured by the following measurement method after dilution to a solid content concentration of 30% by mass or 50% by mass, and the coefficient of variation of the viscosity calculated based on the measurement results is also included. Coefficient of variation of viscosity = (standard deviation / mean value) × 100 (In the formula, the standard deviation is calculated using a shear rate of 0.25 s.) -1 This is the standard deviation (mPa·s) of viscosity at a shear rate of 0.25 s², with the mean value being 0.25 s². -1 This is the average viscosity (mPa·s) in [location]. [Method for measuring viscosity] The viscosity of the aqueous dispersion is measured using a dynamic viscoelasticity analyzer (Anton Paar's "MCR702e MultiDrive"), a temperature control system (Anton Paar's "C-PTD 200"), and a coaxial double-cylinder analyzer (Anton Paar's "C-PTD 200"). First, the aqueous dispersion sample in a bottle is thoroughly shaken to obtain a slurry sample. Next, the obtained slurry sample is injected into a cup container up to the mark using a dropper. At this time, the slurry sample is taken from the bottom of the bottle to avoid the inclusion of air bubbles as much as possible. Subsequently, the cup container containing the slurry sample is placed in the temperature control system, and under a temperature condition of 25°C, the bob attached to the dynamic viscoelasticity analyzer is moved into the cup container containing the slurry sample. After confirming that the bob is completely immersed in the sample, shear rheology measurement is started based on the following measurement conditions. To minimize the effects of slurry sample sedimentation, the process from slurry sample injection to the start of shear rheology measurement should be carried out as quickly as possible. Furthermore, shear rheology measurement should begin at the low strain rate side. [Measurement conditions for shear rheology measurements] Measurement method: Shear rheology measurement (standard vibration, shear rate dependence) Measuring jig: CC27 (coaxial double cylinder, cup inner diameter 28.925 mm) Bob length: 39.993mm Bob diameter: 26.649mm Shear rate: 0.25 sec -1 Measurement temperature: 25℃ Atmospheric gas: Atmosphere Number of measurement points: 21 points Number of measurements: 3

[0128] 2. Method for producing an aqueous dispersion Examples of methods for producing the aqueous dispersion of this disclosure include a method comprising the following steps (1) and (2) in this order. Step (1): In a container, a non-fluorinated surfactant is dissolved in an aqueous solvent, and further, the surface free energy is 70 mJ / m 2 Add particles smaller than a certain size and stir using a stirrer. Step (2): After stirring, ultrasonic treatment is performed, a non-fluorine-based dispersant is added, and ultrasonic treatment is performed again to obtain an aqueous dispersion.

[0129] Details of the aqueous dispersion obtained by the method for producing the aqueous dispersion of this disclosure are as described in "1. Aqueous Dispersion" above, unless otherwise specified.

[0130] In the method for producing the aqueous dispersion of this disclosure, the details of the non-fluorinated surfactant are as described in "1. Aqueous Dispersion" above, unless otherwise specified.

[0131] In the method for producing an aqueous dispersion according to the present disclosure, the surface free energy is 70 mJ / m 2 Details regarding particles smaller than a certain size are as described in "1. Aqueous Dispersion" above, unless otherwise specified.

[0132] In the method for producing the aqueous dispersion of this disclosure, the details of the non-fluorinated dispersant are as described in "1. Aqueous Dispersion" above, unless otherwise specified.

[0133] In the method for producing the aqueous dispersion of this disclosure, the details of the aqueous solvent are as described in "1. Aqueous Dispersion" above, unless otherwise specified.

[0134] In step (1) of this disclosure, the agitator may be, for example, a homogenizer. The rotational speed when using the agitator is usually 300 rpm or more and 20,000 rpm or less. The rotational time when using the agitator is usually 1 minute or more and 60 minutes or less. The temperature when using the agitator is usually 5°C or more and 100°C or less.

[0135] In step (2) of this disclosure, the ultrasonic treatment can be performed using, for example, an ultrasonic homogenizer. The duration of the ultrasonic treatment is usually between 1 minute and 60 minutes. The temperature of the ultrasonic treatment is usually between 5°C and 100°C.

[0136] The non-fluorinated dispersant used in step (2) of this disclosure can be produced, for example, by copolymerizing monomer (a) and monomer (b) in the presence of a chain transfer agent. In this disclosure, the step of copolymerizing monomer (a) and monomer (b) in the presence of a chain transfer agent may also be simply referred to as the "copolymerization step of this disclosure".

[0137] In this disclosure, a wide range of known methods can be used for copolymerizing monomer (a) and monomer (b), including emulsion polymerization, suspension polymerization, bulk polymerization, interfacial polymerization, and solution polymerization. Among these, solution polymerization is preferred.

[0138] In this disclosure, a wide range of known methods can be used as the method for copolymerizing monomer (a) and monomer (b) by solution polymerization. For example, one method involves preparing a monomer mixture by adding an organic solvent to a mixture containing monomer (a) and monomer (b), and then adding a polymerization initiator and a chain transfer agent to the obtained monomer mixture to copolymerize monomer (a) and monomer (b).

[0139] Examples of chain transfer agents in the copolymerization process of this disclosure include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol, 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, octyl mercaptan, dodecyl mercaptan, and 3-mercaptopropionic acid.

[0140] In the copolymerization process of this disclosure, the amount of chain transfer agent used is preferably 0.01 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently advancing polymerization.

[0141] In this disclosure, a wide range of known azo compounds or organic peroxides commonly used in the art can be used as polymerization initiators.

[0142] Examples of azo compounds in this disclosure include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane1-carbonitride), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl1,1'-azobis(1-cyclohexanecarbonylate), dimethyl2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0143] Examples of organic peroxides in this disclosure include benzoyl peroxide, t-butyl peroxy 2-ethyl hexaate, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0144] In this disclosure, the amount of polymerization initiator used is preferably 0.1 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently promoting polymerization.

[0145] In this disclosure, examples of organic solvents include ether compounds, alcohol compounds, amide compounds, ester compounds, ketone compounds, sulfoxide compounds, hydrocarbon compounds, etc., which can be used individually or in combination of two or more.

[0146] Examples of ether compounds in this disclosure include diethyl ether, tetrahydrofuran (THF), and dioxane, which can be used individually or in combination of two or more.

[0147] Examples of alcohol compounds in this disclosure include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc., which can be used individually or in combination of two or more.

[0148] Examples of amide compounds in this disclosure include N,N-dimethylformamide (DMF), N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N-methylcaprolactam, which can be used individually or in combination of two or more.

[0149] Examples of ester compounds in this disclosure include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, dimethyl carbonate, diethyl carbonate, and ethyl lactate, which can be used individually or in combination of two or more.

[0150] Examples of ketone compounds in this disclosure include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone, isophorone, and the like, which can be used individually or in combination of two or more.

[0151] Examples of sulfoxide compounds in this disclosure include dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, and thiophene, which can be used individually or in combination of two or more.

[0152] Examples of hydrocarbon compounds in this disclosure include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, and heptane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane. These can be used individually or in combination of two or more.

[0153] In this disclosure, the amount of organic solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less, based on 100 parts by mass of the total of monomer (a) and monomer (b), from the viewpoint of efficiently promoting polymerization.

[0154] In the copolymerization process of this disclosure, the polymerization reaction is usually carried out in a temperature range of 30°C to 100°C, preferably 40°C to 80°C. In the copolymerization process of this disclosure, the temperature during the polymerization reaction may be constant or may be changed during the polymerization reaction.

[0155] In the copolymerization process of this disclosure, the polymerization reaction time is usually 0.5 hours or more and within 48 hours, preferably 1 hour or more and within 30 hours. In the copolymerization process of this disclosure, the polymerization reaction time means the time from the start of polymerization to the end of polymerization.

[0156] 3. Applications of aqueous dispersions The aqueous dispersions of this disclosure have good dispersibility and can therefore be suitably used in a wide range of applications, including coatings, paints, lubricating films, batteries, electrode materials, coating materials, plating, and catalysts. Details of the aqueous dispersions of this disclosure are as described in "1. Aqueous Dispersions" above, unless otherwise specified.

[0157] Specific applications of the coating agent containing the aqueous dispersion of this disclosure include, for example, coating agents for displays, coating agents for vehicles, coating agents for building materials, coating agents for printing, and coating agents for batteries.

[0158] Specific applications of the coatings containing the aqueous dispersion of this disclosure include, for example, coatings for building materials, automotive coatings, semiconductor coatings, industrial coatings, and structural coatings.

[0159] A lubricating film prepared using the aqueous dispersion of the present disclosure is typically a film consisting of the aqueous dispersion of the present disclosure. Preferably, a lubricating film prepared using the aqueous dispersion of the present disclosure is a film consisting of polytetrafluoroethylene particles or carbon nanotube granules, a non-fluorinated surfactant of the present disclosure, and a non-fluorinated dispersant of the present disclosure.

[0160] Specific applications of batteries manufactured using the aqueous dispersion of this disclosure include, for example, nickel-metal hydride batteries, lithium-ion secondary batteries, sodium-ion secondary batteries, potassium-ion secondary batteries, fuel cells, and the like.

[0161] As one embodiment of the present disclosure, a battery prepared using the aqueous dispersion of the present disclosure preferably comprises a positive electrode, a negative electrode, and an electrode film prepared using the aqueous dispersion of the present disclosure.

[0162] In another embodiment of the present disclosure, a battery prepared using the aqueous dispersion of the present disclosure preferably comprises a positive electrode, a negative electrode, and a gas diffusion layer prepared using the aqueous dispersion of the present disclosure.

[0163] This disclosure provides subject matter in the following aspects: Section 1. Surface free energy is 70 mJ / m 2 It contains particles smaller than a certain size, a non-fluorinated surfactant, and a non-fluorinated dispersant. The content of the non-fluorinated surfactant is such that the surface free energy is 70 mJ / m 2 For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The content of the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m 2 For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The total content of the non-fluorinated surfactant and the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m 2 An aqueous dispersion containing 25 parts by mass or less per 100 parts by mass of particles smaller than a certain size. Section 2. The surface free energy in the total solid content of the aqueous dispersion is 70 mJ / m² 2 The aqueous dispersion according to item 1, wherein the content of particles smaller than 60% by mass is 60% or less. Section 3. The aforementioned surface free energy is 70 mJ / m 2 The aqueous dispersion according to item 1 or 2, wherein the particles less than a certain size are polytetrafluoroethylene particles or carbon nanotube granules. Section 4. The non-fluorinated dispersant comprises a copolymer, The aqueous dispersion according to any one of claims 1 to 3, wherein the copolymer contains a constituent unit (A) derived from a monomer (a) having a phenyl group. Section 5. The aqueous dispersion according to claim 4, wherein the copolymer further contains a constituent unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group. Section 6. The aqueous dispersion according to item 4 or 5, wherein the monomer (a) having a phenyl group is a monomer represented by the following formula (1). [ka] (In the formula, R 1 This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R 2 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R 3 -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O- represent a single bond, -O-, -CH(OH)-, -OC(=O)O-, or -OC(=O)O-. R 4 , R 5 , R 6 , R 7 and R 8 Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R 4 , R 5 , R 6 , R 7 and R 8 (Except when all atoms are hydrogen atoms.) Section 7. The aqueous dispersion according to item 5, wherein the monomer (b) having a hydroxyl group or a phosphate group is a monomer represented by the following formula (2). [ka] (In the formula, R 9This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R 10 This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. n represents a number between 1 and 20 on average. R 10 However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, R 11 This indicates a hydroxyl group or a phosphate group. R 10 However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents, R 11 (This represents a hydrogen atom or a phosphate group.) Section 8. The aqueous dispersion according to any one of claims 1 to 7, wherein the nonfluorinated surfactant is at least one selected from the group consisting of a nonfluorinated nonionic surfactant, a nonfluorinated anionic surfactant, a nonfluorinated cationic surfactant, and a nonfluorinated amphoteric surfactant. Section 9. The aforementioned surface free energy is 70 mJ / m 2 When the solid content concentration of particles smaller than 30% by mass or 50% by mass is set, the viscosity is measured by the following viscosity measurement method, at a shear rate of 0.25 s. -1 The aqueous dispersion according to any one of claims 1 to 8, wherein the coefficient of variation of viscosity in the following formula is preferably less than 28%, more preferably 25% or less, even more preferably 20% or less, and particularly preferably 15% or less. Coefficient of variation of viscosity = (standard deviation / mean value) × 100 (In the formula, the standard deviation is calculated using a shear rate of 0.25 s.) -1 This is the standard deviation (mPa·s) of viscosity at a shear rate of 0.25 s², with the mean value being 0.25 s². -1 This is the average viscosity (mPa·s) in [location]. <Method for measuring viscosity> The viscosity of the aqueous dispersion is measured using a dynamic viscoelasticity analyzer (Anton Paar's "MCR702e MultiDrive"), a temperature control system (Anton Paar's "C-PTD 200"), and a coaxial double-cylinder analyzer (Anton Paar's "C-PTD 200"). First, the aqueous dispersion sample in a bottle is thoroughly shaken to obtain a slurry sample. Next, the obtained slurry sample is injected into a cup container up to the mark using a dropper. At this time, the slurry sample is taken from the bottom of the bottle to avoid the inclusion of air bubbles as much as possible. Subsequently, the cup container containing the slurry sample is placed in the temperature control system, and under a temperature condition of 25°C, the bob attached to the dynamic viscoelasticity analyzer is moved into the cup container containing the slurry sample. After confirming that the bob is completely immersed in the sample, shear rheology measurement is started based on the following measurement conditions. To minimize the effects of slurry sample sedimentation, the process from slurry sample injection to the start of shear rheology measurement should be carried out as quickly as possible. Furthermore, shear rheology measurement should begin at the low strain rate side. <Measurement conditions for shear rheology measurements> Measurement method: Shear rheology measurement (standard vibration, shear rate dependence) Measuring jig: CC27 (coaxial double cylinder, cup inner diameter 28.925 mm) Bob length: 39.993mm Bob diameter: 26.649mm Shear rate: 0.25 sec -1 Measurement temperature: 25℃ Atmospheric gas: Atmosphere Number of measurement points: 21 points Number of measurements: 3 Section 10. A coating agent comprising an aqueous dispersion described in any one of items 1 to 9. Section 11. A paint comprising an aqueous dispersion as described in any one of items 1 to 9. Section 12. A lubricating film prepared using an aqueous dispersion described in any one of items 1 to 9. Section 13. A battery produced using the aqueous dispersion according to any one of Items 1 to 9.

Examples

[0164] Hereinafter, the present disclosure will be described more specifically based on examples, but the present disclosure is not limited to the aspects of these examples. In the following examples and comparative examples, "room temperature" means a temperature within the range of 20°C to 25°C.

[0165] <Measurement Methods and Evaluation Methods> The measurement methods and evaluation methods in the examples and comparative examples are as follows.

[0166] <Evaluation of Dispersibility> The average particle diameter of the aqueous dispersion obtained in each example or each comparative example was measured using a particle diameter measurement apparatus ("Zetasizer Nano ZS" manufactured by Malvern Panalytical) under the following measurement conditions. (Measurement Conditions for Average Particle Diameter of Composite Particle Dispersion) ·Cell: DTS0012 ·Temperature: 25°C ·Measurement time: 60 seconds The average particle diameter of the aqueous dispersion was calculated using data analysis software installed in the particle diameter measurement apparatus. Further, it was confirmed whether the particle size distribution has one peak (unimodal) or two peaks (bimodal). Dispersibility was evaluated according to the following evaluation criteria. In the case of ◯, it was evaluated that the particles were dispersed at the primary particle diameter, and in the case of ×, it was evaluated that the particles were agglomerated. (Evaluation Criteria) ◯: The average particle diameter is within the range of 200 to 300 nm, and the particle size distribution is unimodal ×: The average particle diameter is greater than 300 nm, or the particle size distribution is bimodal

[0167] <Evaluation of Viscosity Reproducibility> Based on the viscosity measurement method described below, the aqueous dispersions obtained in Examples 1 to 5 or Comparative Examples 4 to 6 were measured at a shear rate of 0.25 s -1 to measure the viscosity (mPa·s). [Method for Measuring Viscosity] Viscosity was measured for the aqueous dispersions obtained in Examples 1 to 5 or Comparative Examples 4 to 6 using a dynamic viscoelasticity measuring device ("MCR702e MultiDrive" manufactured by Anton Paar), a temperature control system ("C-PTD 200" manufactured by Anton Paar), and a coaxial double-cylinder measuring system ("C-PTD 200" manufactured by Anton Paar). First, the aqueous dispersion sample placed in a bottle was thoroughly shaken together with the bottle to obtain a slurry sample. Next, the obtained slurry sample was injected with a dropper up to the marked line in the cup container. At this time, the slurry sample was collected from the bottom of the bottle to avoid air bubble entrainment as much as possible. Subsequently, the cup container containing the slurry sample was set in the temperature control system, and under a temperature condition of 25°C, the bob attached to the dynamic viscoelasticity measuring device was moved into the cup container containing the slurry sample. After confirming that the bob was completely immersed in the sample, shear rheology measurement was started based on the following measurement conditions. In order to eliminate the influence of sedimentation of the slurry sample as much as possible, the process from the injection of the slurry sample to the start of the shear rheology measurement was performed as promptly as possible. The shear rheology measurement was started from the low strain rate side. [Measurement Conditions for Shear Rheology Measurement] Measurement method: Shear rheology measurement (standard oscillation, shear rate dependence) Measurement jig: CC27 (coaxial double cylinder, cup inner diameter 28.925 mm) Bob length: 39.993 mm Bob diameter: 26.649 mm Shear rate: 0.25 sec -1 Measurement temperature: 25°C Atmosphere gas: Air Number of measurement points: 21 points Number of measurements: 3 times

[0168] From the viscosity measurement results, the coefficient of variation (%) of viscosity represented by the following formula was calculated, and the reproducibility of viscosity was evaluated according to the following evaluation criteria. In the case of ○, the aqueous dispersion was evaluated as having excellent viscosity reproducibility, and in the case of ×, the aqueous dispersion was evaluated as having poor viscosity reproducibility. Coefficient of variation of viscosity = (standard deviation / mean value) × 100 (In the formula, the standard deviation is calculated using a shear rate of 0.25 s.) -1 This is the standard deviation (mPa·s) of viscosity at a shear rate of 0.25 s², with the mean value being 0.25 s². -1 This is the average viscosity (mPa·s) in [location]. (Evaluation Criteria) ○: The coefficient of variation of viscosity was less than 28%. ×: The coefficient of variation of viscosity was 28% or higher.

[0169] The raw materials used in the examples and comparative examples are as follows: <Non-fluorinated surfactants> • (A-1) Non-fluorinated nonionic surfactant: Polyoxyethylene tridecyl ether ("Neugen TDS-80" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) • (A-2) Non-fluorinated anionic surfactant: Polyoxyethylene alkyl ether phosphate (Phosphanol RS-410 manufactured by Toho Chemical Industry Co., Ltd.) • (A-3) Nonionic surfactant: "TERGITOL® 15-S-9" manufactured by Dow Chemical Company. <Fluorine-based surfactants> • (B-1) "Surflon S242" manufactured by AGC Seimi Chemical Co., Ltd. • (B-2) "U-275" manufactured by Unichem Co., Ltd. • (B-3) "U-276" manufactured by Unichem Co., Ltd.

[0170] (Manufacturing Example 1) <Preparation of non-fluorinated dispersants> In a glass container, 0.022 g of dopamine methacrylamide (DMA) (manufactured by Tokyo Chemical Industry Co., Ltd., 221.26 g / mol) as monomer (a), 2.70 g of polyethylene glycol monoacrylate (n≒4.5) (trade name "Bremmer AE-200", manufactured by NOF Corporation, 270 g / mol) as monomer (b), 0.018 g of 3-mercapto-1,2-propanediol (trade name "1-thioglycerol", Asahi Chemical Industries, Ltd.) as a chain transfer agent, 0.015 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 8.89 g of tetrahydrofuran (THF) as an organic solvent, and 7.89 g of ethanol as an organic solvent were mixed and dissolved at room temperature using a vortex mixer. Next, the container was purged with nitrogen, and polymerization was carried out in a glove box at 55°C for 24 hours. After polymerization, the non-fluorinated dispersant was purified by reprecipitation in hexane, and the purified non-fluorinated dispersant was dried in a vacuum oven (ESPEC Corporation's "Vacuum Oven LHV-112") at 70°C under vacuum conditions for 16 hours to obtain a non-fluorinated dispersant. The obtained non-fluorinated dispersant was used in Examples 1 to 3, but not in Comparative Examples 1 to 6.

[0171] (Manufacturing example 2) <Preparation of non-fluorinated dispersants> In a glass container, 0.022 g of DMA (manufactured by Tokyo Chemical Industry Co., Ltd., 221.26 g / mol) as monomer (a), 5.10 g of polyethylene glycol monoacrylate (n≒6) (trade name "KOREMUL EA-051", manufactured by Hannong Chemicals, 340 g / mol) as monomer (b), 0.034 g of 3-mercapto-1,2-propanediol (trade name "1-thioglycerol", Asahi Chemical Industries, Ltd.) as a chain transfer agent, 0.028 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name "V-65", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, 8.89 g of tetrahydrofuran (THF) as an organic solvent, and 7.89 g of ethanol as an organic solvent were mixed and dissolved at room temperature using a vortex mixer. Then, the container was purged with nitrogen, and polymerization was carried out in a glove box at 55°C for 24 hours. After polymerization, the non-fluorinated dispersant was purified by reprecipitation in hexane, and the purified non-fluorinated dispersant was dried for 16 hours under vacuum conditions at 70°C using a vacuum oven (ESPEC Corporation's "Vacuum Oven LHV-112") to obtain a non-fluorinated dispersant. The obtained non-fluorinated dispersant was used in Examples 4 and 5, but not in Comparative Examples 1 to 6.

[0172] (Example 1) In a glass container, 1.50 g of polyoxyethylene tridecyl ether (Neugen TDS-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 13.2 g of deionized water as a non-fluorine-based nonionic surfactant. Subsequently, the surface free energy was 70 mJ / m 215.0 g of polytetrafluoroethylene (PTFE) particles (primary particle size: 200 nm to 300 nm) ("LeBron L-5" manufactured by Daikin Industries, Ltd.) were added as particles smaller than 150 nm, and the mixture was stirred at 6000 rpm for 4 minutes at room temperature using a homogenizer ("Polytron PT10-35 GT" manufactured by KINEMATICA). Next, the mixture was sonicated for 3 minutes at room temperature using an ultrasonic homogenizer ("SONIFIER 450" manufactured by Branson). Subsequently, 0.30 g of the non-fluorinated dispersant obtained in Production Example 1 was added, and the mixture was sonicated for 2 minutes at room temperature using an ultrasonic homogenizer to prepare an aqueous dispersion (solid content concentration of PTFE particles: 50% by mass).

[0173] (Example 2) An aqueous dispersion (solid content of PTFE particles: 30% by mass) was prepared using the same method as in Example 1, except that 22.1 g of deionized water, 1.00 g of "Neugen TDS-80" as a non-fluorinated nonionic surfactant, 10.0 g of "Lubron L-5" as PTFE particles, and 0.20 g of the non-fluorinated dispersant obtained in Production Example 1 were used.

[0174] (Example 3) An aqueous dispersion (solid content of PTFE particles: 50% by mass) was prepared using the same formulation and method as in Example 1, except that 1.50 g of polyoxyethylene alkyl ether phosphate ester (Phosphanol RS-410, manufactured by Toho Chemical Industry Co., Ltd.) was used as a non-fluorinated anionic surfactant.

[0175] (Example 4) An aqueous dispersion (solid content of PTFE particles: 50% by mass) was prepared using the same formulation and method as in Example 1, except that 0.30 g of the non-fluorinated dispersant obtained in Production Example 2 was used instead of the non-fluorinated dispersant obtained in Production Example 1.

[0176] (Example 5) An aqueous dispersion (solid content concentration of PTFE particles: 30% by mass) was produced in the same manner as in Example 1, except that 0.20 g of the non-fluorine-based dispersant obtained in Production Example 2 was used instead of the non-fluorine-based dispersant obtained in Production Example 1, 1.00 g of "Neugen TDS-80" as a non-fluorine-based nonionic surfactant, 22.1 g of ion-exchanged water, and 10.0 g of "Lublon L-5" which is PTFE particles were used.

[0177] (Comparative Example 1) In a glass container, 1.80 g of a fluorine-based surfactant ("Surflon S242" manufactured by AGC Seimi Chemical Co., Ltd.) was dissolved in 33.2 g of ion-exchanged water. Next, 15.0 g of polytetrafluoroethylene (PTFE) particles (primary particle diameter: 200 nm to 300 nm) ("Lublon L-5" manufactured by Daikin Industries, Ltd.) was added, and the mixture was stirred at 6000 rpm for 4 minutes at room temperature using a homogenizer ("Polytron PT10-35 GT" manufactured by KINEMATICA). Then, ultrasonic treatment was performed at room temperature for 3 minutes using an ultrasonic homogenizer ("SONIFIER 450" manufactured by Branson), thereby producing an aqueous dispersion (solid content concentration of PTFE particles: 30% by mass).

[0178] (Comparative Example 2) An aqueous dispersion (solid content concentration of PTFE particles: 30% by mass) was produced with the same formulation and in the same manner as in Comparative Example 1, except that 26.0 g of ion-exchanged water and 9.00 g of "U-275" manufactured by Unichem Co., Ltd. as a fluorine-based surfactant were used.

[0179] (Comparative Example 3) An aqueous dispersion (solid content concentration of PTFE particles: 30% by mass) was produced with the same formulation and in the same manner as in Comparative Example 1, except that 17.2 g of ion-exchanged water and 18.0 g of "U-276" manufactured by Unichem Co., Ltd. as a fluorine-based surfactant were used.

[0180] (Comparative Example 4) An aqueous dispersion (solid content of PTFE particles: 30% by mass) was prepared using the same formulation and method as in Comparative Example 1, except that 1.80 g of "TERGITOL® 15-S-9" manufactured by Dow Chemical was used as a non-fluorinated surfactant.

[0181] (Comparative Example 5) In a glass container, 1.50 g of polyoxyethylene tridecyl ether (Neugen TDS-80, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), a nonionic surfactant, was dissolved in 33.5 g of deionized water. Next, 15.0 g of PTFE particles (primary particle size 200-300 nm) (product name "Lubron L-5," manufactured by Daikin Corporation) were added, and the mixture was stirred at 6000 rpm for 4 minutes at room temperature using a homogenizer (Polytron PT10-35 GT, manufactured by KINEMATICA). Then, ultrasonic treatment was performed for 3 minutes at room temperature using an ultrasonic homogenizer (SONIFIER 450, manufactured by Branson). After that, ultrasonic treatment was performed again for 2 minutes at room temperature using the ultrasonic homogenizer to prepare an aqueous dispersion (solid content concentration of PTFE particles: 50% by mass).

[0182] (Comparative Example 6) An aqueous dispersion (solid content of PTFE particles: 50% by mass) was prepared using the same formulation and method as in Comparative Example 5, except that 13.5 g of deionized water was used.

[0183] The formulations and results for each example and comparative example are shown in Table 1. In Table 1, "Solid content concentration of PTFE particles in aqueous dispersion" refers to the percentage (mass%) of PTFE particles in the total solid content of the aqueous dispersion.

[0184] [Table 1]

[0185] [Discussion of the results in Table 1] The aqueous dispersions obtained in Examples 1 to 5 all had an average particle size in the range of 200 to 300 nm and a unimodal particle size distribution, confirming their excellent dispersibility. This is thought to be because the non-fluorinated surfactant and the non-fluorinated dispersant obtained in Production Example 1 or 2 adhered to the surface of the PTFE particles, forming composite particles, which reduced the surface tension of the PTFE particles and significantly improved their dispersion performance in the aqueous solvent. The aqueous dispersions obtained in Comparative Examples 1 to 6 did not contain the non-fluorinated dispersant obtained in Production Example 1 or 2, so it is thought that the PTFE particles aggregated in the aqueous solvent. The aqueous dispersions obtained in Examples 1 to 5 all received a "○" rating for viscosity reproducibility compared to the aqueous dispersions obtained in Comparative Examples 1 to 6, confirming that Examples 1 to 5 exhibit excellent viscosity reproducibility.

Claims

1. Surface free energy is 70 mJ / m ２ It contains particles smaller than a certain size, a non-fluorinated surfactant, and a non-fluorinated dispersant. The content of the non-fluorinated surfactant is such that the surface free energy is 70 mJ / m ２ For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The content of the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m ２ For every 100 parts by mass of particles less than 100 parts by mass, the amount is 0.01 parts by mass or more. The total content of the non-fluorinated surfactant and the non-fluorinated dispersant is such that the surface free energy is 70 mJ / m ２ An aqueous dispersion containing 25 parts by mass or less per 100 parts by mass of particles smaller than a certain size.

2. The surface free energy in the total solid content of the aqueous dispersion is 70 mJ / m² ２ The aqueous dispersion according to claim 1, wherein the content of particles smaller than 60% by mass is 60% or less.

3. The aforementioned surface free energy is 70 mJ / m ２ The aqueous dispersion according to claim 1, wherein particles smaller than a certain size are polytetrafluoroethylene particles or carbon nanotube granules.

4. The non-fluorinated dispersant comprises a copolymer, The aqueous dispersion according to claim 1, wherein the copolymer contains a constituent unit (A) derived from a monomer (a) having a phenyl group.

5. The aqueous dispersion according to claim 4, wherein the copolymer further contains a constituent unit (B) derived from a monomer (b) having a hydroxyl group or a phosphate group.

6. The aqueous dispersion according to claim 4, wherein the monomer (a) having a phenyl group is a monomer represented by the following formula (1). 【Chemistry 1】 (In the formula, R １ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. X represents -C(=O)NH- or -C(=O)O-. R ２ This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have single bonds or substituents. R ３ represents a single bond, -O-, -CH(OH)-, -OC(=O)-, or -OC(=O)O-. R ４ , R ５ , R ６ , R ７ and R ８ Each of these independently represents either a hydrogen atom or a hydroxyl group. However, R ４ , R ５ , R ６ , R ７ and R ８ (Except when all atoms are hydrogen atoms.)

7. The aqueous dispersion according to claim 5, wherein the monomer (b) having a hydroxyl group or a phosphate group is a monomer represented by the following formula (2). 【Chemistry 2】 (In the formula, R ９ This represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. R １０ This represents a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, or a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents. n represents a number between 1 and 20 on average. R １０ However, in the case of a linear or branched alkylene group having 1 to 10 carbon atoms, which may have substituents, R １１ This indicates a hydroxyl group or a phosphate group. R １０ However, in the case of a linear or branched oxyalkylene group having 1 to 10 carbon atoms, which may have substituents, R １１ (This represents a hydrogen atom or a phosphate group.)

8. The aqueous dispersion according to claim 1, wherein the nonfluorinated surfactant is at least one selected from the group consisting of nonfluorinated nonionic surfactants, nonfluorinated anionic surfactants, nonfluorinated cationic surfactants, and nonfluorinated amphoteric surfactants.

9. The aforementioned surface free energy is 70 mJ / m ２ When the solid content concentration of particles smaller than 30% by mass or 50% by mass is set to the viscosity measurement method described below, the shear rate is 0.25 s. －１ The aqueous dispersion according to claim 1, wherein the coefficient of variation of the viscosity in the following formula is less than 28%. Coefficient of variation of viscosity = (standard deviation / mean value) × 100 (In the formula, the standard deviation is the shear rate of 0.25 s.) －１ This is the standard deviation (mPa·s) of viscosity at a shear rate of 0.25 s², with the average value being 0.25 s². －１ This is the average viscosity (mPa·s) in [location]. <Method for measuring viscosity> Viscosity of the aqueous dispersion is measured using a dynamic viscoelasticity analyzer (Anton Paar "MCR702e MultiDrive"), a temperature control system (Anton Paar "C-PTD 200"), and a coaxial double-cylinder analyzer (Anton Paar "C-PTD 200"). First, the aqueous dispersion sample in a bottle is thoroughly shaken to obtain a slurry sample. Next, the obtained slurry sample is injected into a cup container up to the mark using a dropper. At this time, the slurry sample is taken from the bottom of the bottle to avoid the inclusion of air bubbles as much as possible. Subsequently, the cup container containing the slurry sample is set in the temperature control system, and under a temperature condition of 25°C, the bob attached to the dynamic viscoelasticity analyzer is moved into the cup container containing the slurry sample. After confirming that the bob is completely immersed in the sample, shear rheology measurement is started based on the following measurement conditions. To minimize the effects of slurry sample sedimentation, the process from slurry sample injection to the start of shear rheology measurement should be carried out as quickly as possible. Furthermore, shear rheology measurement should begin at the low strain rate side. <Measurement conditions for shear rheology measurements> Measurement method: Shear rheology measurement (standard vibration, shear rate dependence) Measuring jig: CC27 (coaxial double cylinder, cup inner diameter 28.925 mm) Bob length: 39.993 mm Bob diameter: 26.649 mm Shear rate: 0.25 sec －１ Measurement temperature: 25℃ Atmospheric gas: Atmosphere Number of measurement points: 21 points Number of measurements: 3

10. A coating agent comprising an aqueous dispersion according to any one of claims 1 to 9.

11. A paint comprising the aqueous dispersion described in any one of claims 1 to 9.

12. A lubricating film prepared using the aqueous dispersion described in any one of claims 1 to 9.

13. A battery manufactured using the aqueous dispersion described in any one of claims 1 to 9.

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