composition

Abstract

To provide a composition containing polymer particles, enabling the formation of a film that excels in defoaming properties, dynamic friction coefficient, and BHM resistance.SOLUTION: A composition according to the present invention contains polymer particles (A), at least one compound (B) selected from the group consisting of sulfate esters having an alkyl group with 10 to 16 carbon atoms and their salts, and a liquid medium (C), wherein the polymer particles (A) contain a polymer having repeating units derived from methyl (meth)acrylate, and a content ratio of the compound (B) is from 10 to 14 pts.mass relative to 100 pts.mass of the polymer particles (A).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition containing polymer particles.

Background Art

[0002] Compositions containing polymer particles such as latex are widely used as binders in paper coating, carpet back sizing, wood products such as plywood and veneer, battery electrodes, tire cord fields, etc. (see, for example, Patent Document 1 and Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Compositions containing such polymer particles are used by mixing with other components in various applications as described above. Therefore, when mixing the composition with other components, a property that can suppress foaming during mixing and can be easily and uniformly mixed (also referred to as "defoaming property" in this specification) is required. Further, when producing a film by mixing the composition with other components, these films are required to have a coefficient of kinetic friction that can suppress the occurrence of scratches even when the surfaces rub against each other during stacked storage. Furthermore, when using the composition by mixing with other components for a floor polish film or the like, a black heel mark resistance (also referred to as "BHM resistance" in this specification) that can suppress the remaining rubber marks of the shoe sole on the coating film is required to be practical.

[0005] Some aspects of the present invention provide a composition containing polymer particles that can produce a film excellent in defoaming properties, as well as excellent in dynamic friction coefficient and BHM resistance.

Means for Solving the Problems

[0006] One aspect of the composition according to the present invention is polymer particles (A), at least one compound (B) selected from the group consisting of sulfates having an alkyl group with 10 to 16 carbon atoms and salts thereof, a liquid medium (C), and a composition containing wherein the polymer particles (A) contain a polymer having a repeating unit derived from methyl (meth)acrylate, and the content ratio of the compound (B) is 10 to 14 parts by mass with respect to 100 parts by mass of the polymer particles (A).

[0007] In one aspect of the composition, the compound (B) may be one selected from the group consisting of dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and salts thereof.

[0008] In any aspect of the composition, the acid value of the polymer constituting the polymer particles (A) may be 30 to 200 mgKOH / g.

Effects of the Invention

[0009] According to the composition of the present invention, it is excellent in defoaming properties and can produce a film excellent in dynamic friction coefficient and BHM resistance.

Modes for Carrying Out the Invention

[0010] Hereinafter, preferred embodiments of the present invention will be described in detail. It should be noted that the present invention is not limited to the following embodiments and includes various modified examples implemented without changing the gist of the present invention.

[0011] In this specification, “(meth)acryl~” represents “acryl~” or “methacryl~”.

[0012] In this specification, the numerical range described using “X~Y” means that it includes numerical value X as the lower limit value and includes numerical value Y as the upper limit value.

[0013] 1. Composition The composition according to one embodiment of the present invention contains polymer particles (A) (hereinafter also referred to as “component (A)”), at least one compound (B) (hereinafter also referred to as “component (B)”) selected from the group consisting of sulfates having an alkyl group with 10 to 16 carbon atoms and salts thereof, and a liquid medium (C) (hereinafter also referred to as “component (C)”). The polymer particles (A) contain a polymer having a repeating unit derived from methyl (meth)acrylate, and the content ratio of the compound (B) is 10 to 14 parts by mass with respect to 100 parts by mass of the polymer particles (A). Hereinafter, the components that can be included in the composition according to this embodiment will be described in detail.

[0014] 1.1. Polymer particles (A) The composition according to this embodiment contains polymer particles (A). The polymer particles (A) contain a polymer having a repeating unit derived from methyl (meth)acrylate. The composition according to this embodiment is preferably in the form of a latex in which the polymer particles (A) are dispersed in the liquid medium (C).

[0015] Hereinafter, the repeating units of the polymer constituting the polymer particles (A), the physical properties of the polymer constituting the polymer particles (A), and the synthesis method will be described in this order.

[0016] 1.1.1. Repeating unit The polymer constituting the polymer particles (A) contains a repeating unit (Ma) derived from methyl (meth)acrylate (hereinafter also referred to as "repeating unit (Ma)"). The polymer constituting the polymer particles (A) preferably further has a repeating unit (Mb) represented by the following general formula (1) (hereinafter also referred to as "repeating unit (Mb)"). [Chemical formula] (In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents an alkyl group having 4 to 10 carbon atoms.)

[0017] When the total of the repeating units contained in the polymer constituting the polymer particles (A) is 100% by mass, the content ratio of the repeating unit (Ma) is preferably 5 to 95% by mass. The lower limit of the content ratio of the repeating unit (Ma) is more preferably 10% by mass, and particularly preferably 15% by mass. The upper limit of the content ratio of the repeating unit (Ma) is more preferably 80% by mass, and particularly preferably 70% by mass.

[0018] Specific examples of the monomer that gives the repeating unit (Mb) include (meth)acrylic acid alkyl (C4-C10) esters such as n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, and decyl (meth)acrylate, and one or more selected from these can be used. Among these (meth)acrylic acid alkyl (C4-C10) esters, it is preferable to be one or more selected from n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.

[0019] The content ratio of the repeating unit (Mb) is preferably 1 to 75% by mass based on 100% by mass of the total repeating units contained in the polymer constituting the polymer particles (A). The lower limit of the content ratio of the repeating unit (Mb) is more preferably 3% by mass, and particularly preferably 5% by mass. The upper limit of the content ratio of the repeating unit (Mb) is more preferably 70% by mass, and particularly preferably 65% by mass.

[0020] In addition to the repeating unit (Ma) and the repeating unit (Mb), the polymer constituting the polymer particles (A) may have a repeating unit derived from another monomer copolymerizable therewith. Examples of such repeating units include repeating units derived from α,β-unsaturated nitrile compounds, repeating units derived from aromatic vinyl compounds, repeating units derived from unsaturated carboxylic acids, repeating units derived from unsaturated carboxylic acid esters (excluding the repeating unit (Ma) and the repeating unit (Mb)), and repeating units derived from α,β-unsaturated amides.

[0021] Specific examples of the α,β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, etc., and one or more selected from these can be used. Among these, it is preferably one or more selected from acrylonitrile and methacrylonitrile, and more preferably acrylonitrile.

[0022] The content ratio of the repeating unit derived from the α,β-unsaturated nitrile compound is preferably 35% by mass or less, and more preferably 3 to 15% by mass based on 100% by mass of the total repeating units contained in the polymer constituting the polymer particles (A).

[0023] Specific examples of the aromatic vinyl compound include, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, 1-ethyl-2-vinylbenzene, divinylbenzene, sodium p-styrenesulfonate, etc., and one or more selected from these can be used. As the aromatic vinyl compound, styrene among the above is particularly preferable.

[0024] When the total of the repeating units contained in the polymer constituting the polymer particles (A) is 100% by mass, the content ratio of the repeating unit derived from the aromatic vinyl compound is 1 to 45% by mass. It is preferably 5 to 30% by mass, more preferably 5 to 30% by mass.

[0025] Specific examples of the unsaturated carboxylic acid include, for example, mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc., and one or more selected from these can be used. In particular, it is preferably one or more selected from acrylic acid, methacrylic acid, and itaconic acid.

[0026] When the total of the repeating units contained in the polymer constituting the polymer particles (A) is 100% by mass, the content ratio of the repeating unit derived from the unsaturated carboxylic acid is preferably 1 to 30% by mass, more preferably 3 to 25% by mass.

[0027] Examples of the unsaturated carboxylic acid ester include (meth)acrylic acid esters other than methyl (meth)acrylate and alkyl (C4-C10) (meth)acrylates. Specific examples of such (meth)acrylic acid esters include ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, ethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like, and one or more selected therefrom can be used.

[0028] The content ratio of the repeating unit derived from the unsaturated carboxylic acid ester (excluding repeating unit (Ma) and repeating unit (Mb)) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on 100% by mass of the total repeating units contained in the polymer constituting the polymer particles (A).

[0029] Specific examples of the α,β-unsaturated amide compound include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and the like, and one or more selected therefrom can be used.

[0030] The content ratio of the repeating unit derived from the α,β-unsaturated amide compound is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, based on 100% by mass of the total repeating units contained in the polymer constituting the polymer particles (A).

[0031] 1.1.2. Physical properties of the polymer 1.1.2.1. Acid value of the polymer The acid value of the polymer constituting the polymer particles (A) is a value measured in accordance with "JIS K 0070:1992", preferably 30 to 200 mgKOH / g, more preferably 35 to 150 mgKOH / g. The acid value of the polymer constituting the polymer particles (A) can be adjusted by the amount of the monomer having an acid group constituting the polymer, etc. The fact that the acid value of the polymer constituting the polymer particles (A) is within the above range indicates that the hydrophilicity of the polymer is low, and the component (B) tends to bleed to the surface during film formation, so that the coefficient of kinetic friction can be reduced. As a result, when the films are stacked and stored, it may be possible to suppress the occurrence of scratches even if the surfaces rub against each other.

[0032] 1.1.2.2. Tetrahydrofuran (THF) insoluble content The THF insoluble content of the polymer constituting the polymer particles (A) is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 9 5% by mass or more, based on 100% by mass of the polymer. The THF insoluble content serves as an index for the solvent resistance and water resistance of the resulting coating film. Therefore, if the THF insoluble content is within the above range, it is considered that the water resistance is good when a coating film is produced using the composition according to this embodiment. The THF insoluble content is measured by the following method.

[0033] <Measurement method of THF insoluble content> 0.15 g of the dry film of the polymer constituting the polymer particles (A) is added to 50 mL of tetrahydrofuran and stirred for 16 hours to obtain a liquid. Then, the liquid is filtered using filter paper corresponding to Type 2 of JIS P3801, 10 mL of the filtrate is collected, dried, and the insoluble content (gel fraction) is calculated from the mass of the dried solid, and the calculated value is taken as the THF insoluble content.

[0034] 1.1.2.3. Number average particle diameter The number average particle diameter of the polymer particles (A) is preferably in the range of 30 nm to 600 nm, more preferably in the range of 40 nm to 200 nm. When the number average particle diameter of the polymer particles (A) is within the above range, the surface of the resulting coating film becomes smooth, and a coating film excellent in scratch resistance can be formed.

[0035] The number average particle diameter of the polymer particles (A) is the value of the particle diameter (D50) at which the cumulative frequency of the number of particles becomes 50% when the particle size distribution is measured using a particle size distribution measuring device based on the light scattering method and the particles are accumulated from the smaller particles. Examples of such particle size distribution measuring devices include Coulter LS230, LS100, LS13 320 (manufactured by Beckman Coulter, Inc.), and FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). These particle size distribution measuring devices can evaluate not only the primary particles of the polymer particles but also the secondary particles formed by the aggregation of the primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an index of the dispersion state of the polymer particles.

[0036] 1.1.2.4. Transition Temperature The transition temperature of the polymer constituting the polymer particles (A) is preferably in the temperature range of -20°C to 150°C, more preferably in the temperature range of -10°C to 135°C, when measured by differential scanning calorimetry (DSC) conforming to JIS K7121:2012.

[0037] 1.1.3. Polymer Synthesis Method The synthesis method of the polymer constituting the polymer particles (A) is not particularly limited, but it can be easily produced, for example, by the emulsion polymerization process shown below.

[0038] The emulsion polymerization process is carried out by radical polymerization with emulsification and dispersion by stirring in the presence of a monomer component, an emulsifier, a polymerization initiator, and a chain transfer agent in an aqueous medium. Hereinafter, each material used in the emulsion polymerization process will be described.

[0039] As the monomer components used in the emulsion polymerization step, in addition to methyl (meth)acrylate, there may be mentioned alkyl (C4-C10) esters of (meth)acrylic acid, α,β-unsaturated nitrile compounds, aromatic vinyl compounds, unsaturated carboxylic acids, unsaturated carboxylic acid esters other than methyl (meth)acrylate and alkyl (C4-C10) esters of (meth)acrylic acid, and α,β-unsaturated amide compounds.

[0040] In 100% by mass of the total monomer components, the content ratio of methyl (meth)acrylate is preferably 5 to 95% by mass, more preferably 10 to 80% by mass, and particularly preferably 15 to 70% by mass.

[0041] In 100% by mass of the total monomer components, the content ratio of alkyl (C4-C10) esters of (meth)acrylic acid is preferably 1 to 75% by mass, more preferably 3 to 70% by mass, and particularly preferably 5 to 65% by mass.

[0042] Specific examples of the emulsifier include, for example, sulfate salts of higher alcohols, aliphatic sulfates, alkylbenzene sulfonates, alkyldiphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, aliphatic phosphate esters, aliphatic phosphates, dehydroabietic acid salts, naphthalene sulfonic acid-formalin condensates, sulfate salts and phosphates having a (poly)alkoxy structure, anionic surfactants such as polymerizable ether sulfate type ammonium salts; nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; fluorine-based surfactants such as perfluorobutyl sulfonate, perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, perfluoroalkyl ethylene oxide adducts, etc., and one or more selected from these can be used.

[0043] Specific examples of the polymerization initiator include, for example, water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate; cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile) and other oil-soluble polymerization initiators, which can be appropriately selected and used. Among these, it is preferable to use potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, or tert-butyl hydroperoxide. The usage ratio of the polymerization initiator is not particularly limited, but it is appropriately set in consideration of combinations such as the monomer composition, the pH of the polymerization reaction system, and other additives.

[0044] Specific examples of the chain transfer agent include, for example, alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-stearyl mercaptan; xanthogen compounds such as dimethyl xanthogen disulfide, diisopropyl xanthogen disulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, styrenated phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide; vinyl ether compounds such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, etc. In addition, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, 2-ethylhexyl thioglycolate, thiomalic acid, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, etc. can be mentioned, and one or more selected from these can be used.

[0045] The emulsion polymerization step is preferably carried out under the conditions that the polymerization temperature is 40 to 80 °C and the polymerization time is 2 to 4 hours.

[0046] After the emulsion polymerization is completed, it is preferable to carry out a neutralization treatment by adding a neutralizing agent so that the pH of the dispersion becomes about 5 to 10. The neutralizing agent to be used is not particularly limited, but examples include metal hydroxides such as sodium hydroxide and potassium hydroxide, and ammonia and amine compounds. By setting the pH of the dispersion in the range of 5 to 10, the formulation stability of the dispersion is It becomes good, but the pH of the dispersion is preferably 6 to 9, more preferably 7 to 8.5. When the total solid concentration in the emulsion polymerization step is 50% by mass or less, the reaction can proceed with good dispersion stability. However, the total solid concentration in the emulsion polymerization step is preferably 45% by mass or less, more preferably 40% by mass or less. Further, by concentrating after the neutralization treatment, high solid content can be achieved while further improving the stability of the particles.

[0047] 1.2. Compound (B) The composition according to this embodiment contains at least one compound (B) selected from the group consisting of a sulfate ester having an alkyl group having 10 to 16 carbon atoms and a salt thereof.

[0048] Examples of the component (B) include alkyl (C10-C16) sulfate ester, alkyl (C10-C16) ether sulfate ester, polyoxyethylene alkyl (C10-C16) ether sulfate ester, alkyl (C10-C16) benzene sulfonic acid, alpha-sulfo fatty acid (C10-C16) ester, and salts thereof. Among these, alkyl (C10-C16) sulfate ester and salts thereof are preferable, and more preferably one selected from the group consisting of dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and salts thereof. Examples of the counter ion forming the salt include monovalent cations such as Li + , Na + , K + , NH4 + and the like. Here, “(C10-C16)” represents that the number of carbon atoms in the structure described immediately before is 10 to 16. These components (B) may be used alone or in combination of two or more.

[0049] In the composition according to this embodiment, the content ratio of component (B) is 10 to 14 parts by mass, preferably 10 to 13 parts by mass, relative to 100 parts by mass of component (A). When the content ratio of component (B) in the composition according to this embodiment is within the above range, the defoaming property of the composition is improved. Further, when the content ratio of component (B) in the composition according to this embodiment is within the above range, since an appropriate amount of component (B) bleeds to the film surface during film formation, a film excellent in dynamic friction coefficient and BHM resistance can be produced.

[0050] Note that component (B) in the composition according to this embodiment may be the same as the component generally used as an emulsifier when polymer particles (A) are synthesized by emulsion polymerization. For this reason, it is presumed that a very small amount of component (B) is contained in the dispersion of polymer particles (A) synthesized by emulsion polymerization. On the other hand, in the present invention, since component (B) is added in a large amount exceeding the amount of the emulsifier used during emulsion polymerization at the stage of preparing the composition, the content of component (B) is in a range significantly larger than the content used during emulsion polymerization.

[0051] 1.3. Liquid medium (C) The composition according to this embodiment contains a liquid medium (C). As the liquid medium (C), an aqueous medium containing water is preferable. The aqueous medium can contain a non-aqueous medium other than water. Examples of such non-aqueous media include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, sulfone compounds, etc., and one or more selected from these can be used. When the liquid medium (C) contains water and a non-aqueous medium, when the total mass of the liquid medium (C) is 100% by mass, it is preferable that 90% by mass or more is water, and more preferably 98% by mass or more is water. By using an aqueous medium as the liquid medium (C) in the composition according to this embodiment, the degree of adverse impact on the environment is reduced, and the safety for handling workers is also increased.

[0052] The content ratio of the non-aqueous medium contained in the aqueous medium is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably substantially not contained in 100% by mass of the aqueous medium. Here, "substantially not contained" means that the non-aqueous medium is not intentionally added as a liquid medium, and it may include a non-aqueous medium that is unavoidably mixed in when preparing the composition. That is, it means that the non-aqueous medium is not intentionally added as a liquid medium, and it may include a non-aqueous medium that is unavoidably mixed in when preparing the composition.

[0053] 1.4. Other Additives The composition according to this embodiment can contain additives other than the above-described components as necessary. Examples of such additives include thickeners, fillers, preservatives, and pH adjusters.

[0054] <Thickener> Examples of the thickener include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; polycarboxylic acids such as poly(meth)acrylic acid and modified poly(meth)acrylic acid; alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol-based (co)polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymer; and water-soluble polymers such as saponified products of copolymers of unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, and fumaric acid and vinyl esters. Among these, alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly(meth)acrylic acid are particularly preferred.

[0055] Examples of commercially available products of these thickeners include alkali metal salts of carboxymethyl cellulose such as CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (all manufactured by Daicel Corporation).

[0056] When the composition according to this embodiment contains a thickener, the usage ratio of the thickener is preferably 5% by mass or less, more preferably 0.1 to 3% by mass, based on the total solid content of the composition.

[0057] <Filler The composition according to this embodiment may improve the hardness of the coating film when formed into a coating film by containing a filler. Examples of the filler include organic fillers and inorganic fillers. Specific examples of the organic filler include polyamide fine particles such as nylon 6, nylon 12, and nylon 66; fluorine-based fine particles such as tetrafluoroethylene and vinylidene fluoride; olefin-based fine particles such as polyethylene and polypropylene; polyester-based fine particles such as polyethylene terephthalate and polyethylene naphthalate; crosslinked particles such as divinylbenzene and polyfunctional acrylate; and rubber fine particles such as natural rubber, isoprene rubber, and acrylic rubber. Specific examples of the inorganic filler include fused spherical silica, fumed silica, sol-gel silica, aluminum oxide, aluminum hydroxide, calcium carbonate, calcium hydroxide, barium sulfate, barium carbonate, magnesium oxide, magnesium hydroxide, and other inorganic fillers derived from minerals such as talc and mica. One or more of these can be used.

[0058] <Preservative The composition according to this embodiment can suppress the growth of bacteria, mold, etc. and the generation of foreign substances when the composition is stored by containing a preservative. Specific examples of the preservative include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, N-n-butyl-1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, etc. One or more of these can be used.

[0059] <pH adjuster The composition according to this embodiment may adjust the pH to 5 to 9 by adding a pH adjuster. By adjusting the pH to 5 to 9, the dispersion stability of the polymer particles (A) may be improved, and the storage stability may be excellent. Examples of the pH adjuster include acidic compounds such as hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, and formic acid; and basic compounds such as potassium hydroxide, ethylenediamine, monoethanolamine, TMAH (tetramethylammonium hydroxide), TEAH (tetraethylammonium hydroxide), and ammonia.

[0060] In the present invention, pH refers to the hydrogen ion exponent, and its value can be measured using a commercially available pH meter (for example, a desktop pH meter manufactured by Horiba, Ltd.) under the conditions of 25°C and 1 atm.

[0061] 1.5. Method for producing the composition The composition according to this embodiment may be produced by mixing the above components, for example, using the method described in JP-A-2007-332202.

[0062] 2. Examples Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" are based on mass unless otherwise specified.

[0063] 2.1. Preparation of a dispersion containing polymer particles (A) 2.1.1. Preparation of dispersion P-1 After sufficiently purging the inside of a separable flask with a capacity of 0.5 L with nitrogen, 100.0 parts by mass of ion-exchanged water and 0.3 parts by mass of ammonium persulfate (APS) were charged. While stirring, the internal temperature was adjusted to 80°C. Separately, in a separate container, 60.0 parts by mass of ion-exchanged water, 48.0 parts by mass of methyl methacrylate (MMA), 39.0 parts by mass of butyl acrylate (BA), 13.0 parts by mass of methacrylic acid (MAA), 2.4 parts by mass of sodium dodecyl sulfate (SDS, manufactured by Kao Corporation, trade name "Emal 2FG"), and 1 part by mass of SR-1025 (manufactured by ADEKA Corporation, trade name "Adekaria Soap SR-1025", ammonium salt of α-sulfo-ω-(1-alkoxy)methyl-2-(2-propenyloxy)ethoxy-poly(oxy-1,2-ethanediyl)) were mixed and stirred to form an emulsion. The obtained emulsion was continuously dropped into the above reaction vessel over 3 hours. After completion of the dropping, stirring was continued at 80°C for 3 hours and then cooled to 40°C to obtain a dispersion P-1 containing 39% polymer particles. The acid value of the polymer particles contained in the dispersion P-1 thus obtained was measured in accordance with JIS K 0070:1992. The results are shown in Table 1.

[0064] 2.1.2. Preparation of Dispersions P-2 to P-5 In the above "2.1.1. Preparation of Dispersion P-1", dispersions P-2, P-3, P-4, and P-5 each containing 39% polymer particles were obtained in the same manner except that the types and amounts of the monomers, polymerization initiator, and emulsifier were changed as shown in Table 1 below.

[0065] 2.2. Examples 1 to 8, Comparative Examples 1 to 6 2.2.1. Preparation of Compositions Each component was mixed so as to have the content ratios described in Table 2 to Table 3 below, and water was added so that the total amount of the components described in Table 2 to Table 3 became 35% by mass, and the compositions of each example and each comparative example were prepared respectively.

[0066] 2.2.2. Evaluation of Defoaming Property When the composition is mixed with other components, if there is intense foaming during mixing, it may not be possible to mix uniformly and it may not be usable in practice. Also, when filling the packaging container, if there is intense foaming, the foam may overflow, and it may not be possible to fill a predetermined amount. Therefore, when the composition is mixed with other components, a property that suppresses foaming during mixing and allows for easy and uniform mixing is required. For this reason, the defoaming property was evaluated by the following method. (Evaluation method) 20 g of the composition prepared above was weighed into a cylindrical glass bottle with a diameter of 3.5 cm, a height of 11 cm, and a volume of 100 mL, sealed with a lid, then shaken up and down 10 times and left standing for 60 minutes. After that, the height of the generated foam from the liquid surface was measured and evaluated according to the following criteria. The results are shown together in Table 2 to Table 3 below. (Evaluation criteria) A: The height from the liquid surface of the foam is less than 4 cm, and it is judged to be good because it can be put into practical use. B: The height from the liquid surface of the foam is 4 cm or more, and it is judged to be poor because it is difficult to put into practical use.

[0067] 2.2.3. Evaluation of dynamic friction coefficient When the composition is mixed with other components to prepare a coating film, etc., if the dynamic friction coefficient of the coating film becomes large, when the formed films are stacked and stored, etc., the films may rub against each other and the surface may be scratched, and it may not be usable in practice. For this reason, the dynamic friction coefficient was evaluated by the following method. (Evaluation method) After adding an aqueous ammonia solution with a concentration of 10% to 100 g of the composition prepared above and adjusting the pH to 7.0, 15 g of butyl carbitol was added and stirred for 2 hours to prepare a composition for evaluating the dynamic friction coefficient. The composition for evaluation thus obtained was applied to a PET film so that the film thickness became 10 μm, and then dried at 80°C for 5 minutes to prepare an evaluation sample. Furthermore, the dynamic friction coefficient of the obtained evaluation sample was evaluated using a surface property measuring instrument (manufactured by Shin-Tech Co., Ltd., Tribogear TYPE: 14FW). The results are shown together in Table 2 to Table 3 below. (Evaluation criteria) AA: The dynamic friction coefficient is 0.4 or less, there are no restrictions on the components mixed during the preparation of the coating film, and it can be put into practical use, so it is judged to be particularly good. A: The dynamic friction coefficient is more than 0.4 to 0.6 or less, and it can be put into practical use, so it is judged to be very good. B: The dynamic friction coefficient is more than 0.6 to 0.8 or less. Although attention needs to be paid to the components mixed during the preparation of the coating film, it can be put into practical use, so it is judged to be good. C: The dynamic friction coefficient is more than 0.8, and it is difficult to put into practical use, so it is judged to be poor.

[0068] 2.2.4. Evaluation of black heel mark (BHM) resistance When the composition is mixed with other components according to the application and used for floor polish films, etc., rubber marks of the shoe sole tend to remain on the coating film, and it may not be possible to maintain a good appearance and may not be usable in practice. Therefore, the black heel mark (BHM) resistance was evaluated by the following method. (Evaluation method) 24 g of ion-exchanged water, 14 g of zinc oxide, 12 g of ammonium carbonate, 20 g of aminoacetic acid, and 30 g of 25% aqueous ammonia were mixed in advance to prepare a Zn chelate solution. The Zn chelate solution was added so that 0.5 chemical equivalent of Zn was contained with respect to the unsaturated carboxylic acid (acrylic acid or methacrylic acid) used as the monomer in the preparation of the dispersion containing the polymer particles (A) in 100 g of the composition prepared above. After stirring for 2 hours, diethylene glycol monoethyl ether and tri(2-n-butoxyethyl) phosphate were mixed at a ratio of 4:1 (mass ratio) to adjust the minimum film-forming temperature (MFT) to 5 °C or lower. Then, ion-exchanged water was added so that the solid content became 19% by mass to prepare a composition for evaluating black heel mark (BHM) resistance. The composition for evaluation thus obtained was applied at a coating amount of 10 g / m 2The operation of applying it onto a homogeneous style (manufactured by Toyobo Co., Ltd., product number "MS Plane MS5626") and drying at 23°C for 1 hour was repeated three times to prepare a sample for evaluation. This sample for evaluation was installed as a floor material at a location with a high pedestrian flow (traffic volume = 50 - 100 people / day) for 10 days, and the degree of adhesion of black heel marks (BHM) was visually observed and evaluated according to the following criteria. The results are shown together in Table 2 to Table 3 below. (Evaluation Criteria) AA: The number of BHM is 20 or less, there are no restrictions considered for the components mixed during the preparation of the coating film, and it is judged to be particularly good because it can be put into practical use. A: The number of BHM is 21 - 40, and it is judged to be very good because it can be put into practical use. B: The number of BHM is 41 - 60, and although attention needs to be paid to the components mixed during the preparation of the coating film, it is judged to be good because it can be put into practical use. C: The number of BHM is 61 or more, and it is judged to be defective because it is difficult to put into practical use.

[0069] 2.3. Evaluation Results Table 1 below shows the components used when preparing dispersions P-1 to P-5 containing polymer particles (A), and the acid value of the polymer particles. Tables 2 to 3 below show the composition of the compositions used in each example and each comparative example and each evaluation result.

[0070] [Table 1]

[0071] [Table 2]

[0072] [Table 3]

[0073] The abbreviations of each component in Table 1 and Table 2 above represent the following products or reagents respectively. <Monomer> · MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name "Acryester M") · EHA: 2-Ethylhexyl acrylate (manufactured by Mitsubishi Chemical Corporation, trade name "Acrylic acid - 2-ethylhexyl") · BA: Butyl acrylate (manufactured by Mitsubishi Chemical Corporation, trade name "Butyl acrylate") · ST: Styrene (manufactured by NS Styrene Monomer Co., Ltd., trade name "Styrene monomer") · EDMA: Ethylene glycol dimethacrylate (manufactured by Mitsubishi Chemical Corporation, trade name "Acryester ED") · AA: Acrylic acid (manufactured by Toagosei Co., Ltd., trade name "Acrylic acid") · MAA: Methacrylic acid (manufactured by Mitsubishi Chemical Corporation, trade name "MAA") <Polymerization initiator> · APS: Ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name "Ammonium persulfate") · SPS: Sodium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc., trade name "Sodium persulfate") <Emulsifier> · SDS: Sodium dodecyl sulfate (manufactured by Kao Corporation, trade name "Emal 2FG", carbon number of alkyl group = 12) · SR-1025: Manufactured by ADEKA Corporation, trade name "Adekaria soap SR-1025", ammonium salt of α-sulfo-ω-(1-alkoxy)methyl-2-(2-propenyloxy)ethoxy-poly(oxy-1,2-ethanediyl)) <Compound (B)> · SDS: Sodium dodecyl sulfate (manufactured by Kao Corporation, trade name "Emal 2FG", carbon number of alkyl group = 12) · ADS: Ammonium dodecyl sulfate (manufactured by Kao Corporation, trade name "Latemul AD-25", carbon number of alkyl group = 12) · STS: Sodium tetradecyl sulfate (manufactured by Nikko Chemicals Co., Ltd., trade name "NIKKOL SMS - F", carbon number of alkyl group = 14) · SHS: Sodium hexadecyl sulfate (manufactured by Nikko Chemicals Co., Ltd., trade name "NIKKOL SCS", number of carbon atoms in the alkyl group = 16) <Other additives> · SES: Sodium 2-ethylhexyl sulfate (manufactured by Sanyo Chemical Industries, Ltd., trade name "Sandet ONA", number of carbon atoms in the alkyl group = 8) · SOS: Sodium octadecyl sulfate (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Sodium Octadecyl Sulfate", number of carbon atoms in the alkyl group = 18)

[0074] According to the evaluation results in Table 2 to Table 3 above, it was found that the compositions according to the present invention shown in Examples 1 to 8 are excellent in defoaming properties and can form a film excellent in dynamic friction coefficient and BHM resistance. The compositions shown in Comparative Examples 1 to 6 contain less than 10 parts by mass or more than 14 parts by mass of component (B) with respect to 100 parts by mass of polymer particles (A), and it was found that they do not satisfy all of the defoaming property, dynamic friction coefficient, and BHM resistance.

[0075] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes a configuration that is substantially the same as the configuration described in the embodiment (for example, a configuration having the same functions, methods, and results, or a configuration having the same objectives and effects). Further, the present invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. Further, the present invention includes a configuration having the same operational effects as the configuration described in the embodiment or a configuration capable of achieving the same objective. Further, the present invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

Claims

1. Polymer particles (A), at least one compound (B) selected from the group consisting of sulfates having an alkyl group with 10 to 16 carbon atoms and salts thereof, a liquid medium (C), and a composition containing the same, wherein the polymer particles (A) contain a polymer having a repeating unit derived from methyl (meth)acrylate, and the content ratio of the compound (B) is 10 to 14 parts by mass with respect to 100 parts by mass of the polymer particles (A).

2. The composition according to claim 1, wherein the compound (B) is one selected from the group consisting of dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and salts thereof.

3. The composition according to claim 1 or claim 2, wherein the acid value of the polymer constituting the polymer particles (A) is 30 to 200 mgKOH / g.

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