Composition

Abstract

To provide a composition containing polymer particles, which suppresses cissing during coating, is excellent in blocking resistance and dynamic friction coefficient, and can produce a coating film having a good appearance with suppressed haze in particular.SOLUTION: The composition according to the present invention contains polymer particles (A), silicone particles (B), and a liquid medium (C), wherein the polymer particles (A) have a repeating unit (Ma) derived from methyl (meth) acrylate and a repeating unit (Mb) derived from an unsaturated carboxylic acid, and the number average particle size of the polymer particles (A) is smaller than the number average particle size of the silicone particles (B).SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Compositions containing polymer particles such as latex are widely used as binders in fields such as paper coating, carpet backsizing, wood products such as plywood and veneer, battery electrodes, and tire cords (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-38908 [Patent Document 2] International Publication No. 2017 / 168817 Summary of the Invention [Problem to be solved by the invention]

[0004] Compositions containing such polymer particles are used in a mixture with other components in various applications such as those described above. For example, when a mixture of the composition and other components is applied to a substrate to form a coating film, it is necessary to suppress repelling during application and form a homogeneous coating film. Furthermore, when substrates on which a coating film has been formed are stored in a stacked state, blocking resistance sufficient to prevent scratches from occurring when the substrate surfaces are rubbed against each other and a reduced dynamic friction coefficient of the coating film are required to prevent surface scratches from occurring due to rubbing of the coating films against each other. Furthermore, to improve the appearance of the coating film, it is necessary to suppress the haze of the coating film.

[0005] Some aspects of the present invention provide a composition containing polymer particles that can produce a coating film that suppresses cissing during application, is excellent in blocking resistance and dynamic friction coefficient, and has a good appearance, particularly with reduced haze. [Means for solving the problem]

[0006] One aspect of the composition of the present invention is A composition comprising polymer particles (A), silicone particles (B), and a liquid medium (C), the polymer particles (A) have repeating units (Ma) derived from methyl (meth)acrylate and repeating units (Mb) derived from an unsaturated carboxylic acid, The number average particle size of the polymer particles (A) is smaller than the number average particle size of the silicone particles (B).

[0007] In one embodiment of the composition, The silicone particles (B) may have a repeating unit derived from a cyclic silicone.

[0008] In any of the above-described embodiments of the composition, The number average particle diameter of the polymer particles (A) may be 30 nm to 600 nm.

[0009] In any of the above-described embodiments of the composition, The silicone particles (B) may be contained in an amount of 2 to 60 parts by mass relative to 100 parts by mass of the polymer particles (A). [Effects of the Invention]

[0010] The composition of the present invention can produce a coating film that suppresses cissing during application, has excellent blocking resistance and dynamic friction coefficient, and has a good appearance with particularly suppressed haze. DETAILED DESCRIPTION OF THE INVENTION

[0011] Preferred embodiments of the present invention will be described in detail below. Note that the present invention is not limited to the following embodiments, and various modifications are also included within the scope of the present invention.

[0012] In this specification, "(meth)acrylic" refers to "acrylic" or "methacrylic".

[0013] In this specification, a numerical range described using "X to Y" means that the range includes the numerical value X as the lower limit and the numerical value Y as the upper limit.

[0014] 1. Composition A composition according to one embodiment of the present invention is a composition containing polymer particles (A), silicone particles (B), and a liquid medium (C), wherein the polymer particles (A) have repeating units (Ma) derived from methyl (meth)acrylate and repeating units (Mb) derived from an unsaturated carboxylic acid, and the number average particle diameter of the polymer particles (A) is smaller than the number average particle diameter of the silicone particles (B). Components that may be contained in the composition according to this embodiment will be described in detail below.

[0015] 1.1. Polymer particles (A) The composition according to this embodiment contains polymer particles (A). The composition according to this embodiment is preferably in the form of a latex in which the polymer particles (A) are dispersed in a liquid medium (C).

[0016] Hereinafter, the repeating units contained in 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 that order.

[0017] 1.1.1. Repeating Unit The polymer constituting the polymer particles (A) has a repeating unit (Ma) (hereinafter also referred to as "repeating unit (Ma)") derived from methyl (meth)acrylate and a repeating unit (Mb) (hereinafter also referred to as "repeating unit (Mb)") derived from an unsaturated carboxylic acid.

[0018] When the total amount of repeating units contained in the polymer particles (A) is taken as 100% by mass, the lower limit of the content of the repeating unit (Ma) is preferably 20% by mass, more preferably 30% by mass. The upper limit of the content of the repeating unit (Ma) is preferably 90% by mass, more preferably 85% by mass. When the polymer particles (A) contain the repeating unit (Ma) within the above range, the coating strength is improved and good blocking resistance is exhibited.

[0019] Specific examples of unsaturated carboxylic acids that provide the repeating unit (Mb) include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and the repeating unit (Mb) may be one or more selected from these. In particular, one or more selected from acrylic acid, methacrylic acid, and itaconic acid are preferred.

[0020] When the total amount of repeating units contained in the polymer particles (A) is taken as 100% by mass, the lower limit of the content of the repeating unit (Mb) is preferably 1% by mass, more preferably 2% by mass. The upper limit of the content of the repeating unit (Mb) is preferably 20% by mass, more preferably 15% by mass. When the polymer particles (A) contain the repeating unit (Mb) within the above range, the particle surface is negatively charged and stabilized, making it less likely to cissing.

[0021] In addition to the repeating units (Ma) and (Mb), the polymer particles (A) may contain repeating units derived from other monomers copolymerizable therewith, such as repeating units derived from α,β-unsaturated nitrile compounds, repeating units derived from aromatic vinyl compounds, repeating units derived from unsaturated carboxylic acid esters (excluding the repeating units (Ma)), and repeating units derived from α,β-unsaturated amides.

[0022] Specific examples of the α,β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, etc., and the compound may be one or more selected from these. Among these, the compound may be one or more selected from acrylonitrile and methacrylonitrile, and more preferably acrylonitrile.

[0023] The content of repeating units derived from the α,β-unsaturated nitrile compound is preferably 35% by mass or less, and more preferably 3 to 15% by mass, when the total amount of repeating units contained in the polymer particles (A) is taken as 100% by mass.

[0024] Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, 1-ethyl-2-vinylbenzene, divinylbenzene, sodium p-styrenesulfonate, etc., and the aromatic vinyl compound may be one or more selected from these. Of the above, styrene is particularly preferred as the aromatic vinyl compound.

[0025] The content of repeating units derived from aromatic vinyl compounds is preferably 5 to 45 mass%, and more preferably 10 to 30 mass%, when the total amount of repeating units contained in the polymer particles (A) is taken as 100 mass%.

[0026] Examples of the unsaturated carboxylic acid ester include (meth)acrylic acid esters other than methyl (meth)acrylate. Specific examples of the (meth)acrylic acid ester include alkyl (C4-C10) (meth)acrylate 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; ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, benzyl (meth)acrylate, hydroxymethyl (meth)acrylate; and Examples include hydroxyethyl acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl (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 ethylene di(meth)acrylate, and the monomer may be one or more selected from these.

[0027] The content of the repeating units derived from the unsaturated carboxylic acid ester (excluding the repeating unit (Ma)) is preferably 1 to 75 mass %, and more preferably 5 to 65 mass %, when the total of the repeating units contained in the polymer particles (A) is taken as 100 mass %. When the polymer particles (A) contain the repeating units derived from the unsaturated carboxylic acid ester (excluding the repeating unit (Ma)) within the above range, the properties as a binder are more easily exhibited, and a good coating film may be produced.

[0028] Specific examples of the α,β-unsaturated amide compound include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, etc., and one or more selected from these can be used.

[0029] When the total of the repeating units contained in the polymer particles (A) is 100% by mass, the content ratio of the repeating unit derived from the α,β-unsaturated amide compound is preferably 0.1 to 20% by mass, and more preferably 0.5 to 15% by mass.

[0030] 1.1.2. Physical properties of the polymer particles (A) 1.1.2.1. Tetrahydrofuran (THF) insoluble matter The THF insoluble matter of the polymer particles (A) is preferably 60% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more with respect to 100% by mass of the polymer particles (A). The THF insoluble matter serves as an index for the solvent resistance and water resistance of the resulting coating film. Therefore, if the THF insoluble matter of the polymer particles (A) is within the above range, it is considered that the water resistance when a coating film is produced using the composition according to the present embodiment is good. The THF insoluble matter is measured by the following method.

[0031] <Measurement method of THF insoluble matter> 0.15 g of the dry film of 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 a filter paper corresponding to Type 2 of JIS P3801, 10 mL of the filtrate is collected, dried, and the insoluble matter (gel fraction) is calculated from the dried mass, and the calculated value is taken as the THF insoluble matter.

[0032] 1.1.2.2. Number average particle diameter In the present invention, the number average particle size of the polymer particles (A) must be smaller than the number average particle size of the silicone particles (B). When the number average particle size of the polymer particles (A) is smaller than the number average particle size of the silicone particles (B), the surface of the resulting coating film is more likely to be smooth, reducing the friction resistance of the coating film surface and enabling the production of a coating film with excellent blocking resistance. Furthermore, when the number average particle size of the polymer particles (A) is smaller than the number average particle size of the silicone particles (B), light scattering is more likely to be reduced, resulting in reduced coating film haze.

[0033] 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 in the above range, the surface of the resulting coating film tends to be smooth, and a coating film with excellent blocking resistance can be produced.

[0034] The number average particle size of the polymer particles (A) is the particle size (D50) at which the cumulative frequency of the number of particles when accumulating particles starting from the smallest particle is 50% when the particle size distribution is measured using a particle size distribution measuring device that uses light scattering as the measurement principle. Examples of such particle size distribution measuring devices include Coulter LS230, LS100, and LS13 320 (all manufactured by Beckman Coulter, Inc.) and FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). These particle size distribution measuring devices can evaluate not only primary particles of polymer particles but also secondary particles formed by aggregation of 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 polymer particles.

[0035] 1.1.2.3.Transition Temperature The transition temperature of the polymer particles (A) is preferably in the temperature range of -20°C to 150°C, more preferably -10°C to 135°C, when measured by differential scanning calorimetry (DSC) in accordance with JIS K7121:2012.

[0036] 1.1.3. Method for synthesizing polymer particles (A) The method for synthesizing the polymer particles (A) is not particularly limited, but they can be easily prepared, for example, by the emulsion polymerization process described below.

[0037] The emulsion polymerization step is carried out by emulsifying and dispersing the monomer components, an emulsifier, a polymerization initiator, and a chain transfer agent in an aqueous medium by stirring, followed by radical polymerization. Each material used in the emulsion polymerization step will be described below.

[0038] Examples of the monomer components used in the emulsion polymerization step include methyl (meth)acrylate and unsaturated carboxylic acids, as well as α,β-unsaturated nitrile compounds, aromatic vinyl compounds, unsaturated carboxylic acid esters other than methyl (meth)acrylate, and α,β-unsaturated amide compounds.

[0039] The content of methyl (meth)acrylate in 100% by mass of all monomer components is preferably from 20 to 90% by mass, and more preferably from 30 to 85% by mass.

[0040] The content of the unsaturated carboxylic acid in 100% by mass of all the monomer components is preferably 1 to 20% by mass, and more preferably 2 to 15% by mass.

[0041] The content of unsaturated carboxylic acid esters other than methyl (meth)acrylate in 100% by mass of all monomer components is preferably 1 to 75% by mass, and more preferably 5 to 65% by mass.

[0042] Specific examples of the emulsifier include anionic surfactants such as sulfate salts of higher alcohols, aliphatic sulfates, alkylbenzenesulfonates, alkyldiphenyletherdisulfonates, aliphatic sulfonates, aliphatic carboxylates, aliphatic phosphate salts, aliphatic phosphate salts, dehydroabietic acid salts, naphthalenesulfonic acid-formalin condensates, sulfate salts or phosphate salts having a (poly)alkoxy structure, and polymerizable ether sulfate-type ammonium salts; nonionic surfactants such as alkyl esters of polyethylene glycol, alkylphenyl ethers of polyethylene glycol, and alkyl ethers of polyethylene glycol; and fluorine-based surfactants such as perfluorobutylsulfonates, perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, and perfluoroalkylethylene oxide adducts. One or more selected from these may be used.

[0043] Specific examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate; cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylpropionamidine; Oil-soluble polymerization initiators such as tert-butyl hydroperoxide, azobisisobutyronitrile, and 1,1'-azobis(cyclohexanecarbonitrile) can be appropriately selected and used. Among these, potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, or tert-butyl hydroperoxide is preferably used. The proportion of the polymerization initiator used is not particularly limited, but is appropriately set in consideration of the monomer composition, the pH of the polymerization reaction system, the combination of other additives, and the like.

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

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

[0046] After the emulsion polymerization is completed, it is preferable to neutralize the dispersion by adding a neutralizing agent so that the pH of the dispersion is about 5 to 10. The neutralizing agent used is not particularly limited, but examples include metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, and amine compounds. Setting the pH of the dispersion in the range of 5 to 10 improves the blend stability of the dispersion, and the pH of the dispersion is preferably 6 to 9, and more preferably 7 to 8.5. Setting the total solids concentration in the emulsion polymerization step to 50% by mass or less allows the reaction to proceed with good dispersion stability, but the total solids concentration in the emulsion polymerization step is preferably 45% by mass or less, and more preferably 40% by mass or less. Furthermore, concentration after the neutralization treatment can further improve particle stability while achieving a high solids concentration.

[0047] 1.2. Silicone particles (B) The composition according to this embodiment contains silicone particles (B). The silicone particles (B) are particles whose main component is a silicone resin. The silicone particles (B) can be obtained by polymerizing a silicone component such as a siloxane compound or an alkoxysilane compound. The silicone particles (B) may contain a monomer other than the silicone component as a constituent component, but the silicone particles (B) preferably contain a silicone component as a monomer in an amount of 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more.

[0048] Examples of the siloxane compound include cyclic siloxane compounds, linear siloxane compounds, branched siloxane compounds, etc. Among these, examples of the cyclic siloxane compound include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc.

[0049] As the alkoxysilane compound, a silane compound having one or more alkoxy groups in the molecule can be used, and examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, etc., as well as silane coupling agents such as vinylmethyldimethoxysilane, γ-(meth)acryloyloxytrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-glycidoxypropyltrimethoxysilane.

[0050] These silicone components can be used alone or in combination of two or more. Furthermore, during polymerization of the silicone particles (B), an emulsifier, catalyst, neutralizer, etc. may be appropriately added. The average molecular weight of the silicone resin constituting the silicone particles (B) is preferably 10,000 or more, more preferably 50,000 or more.

[0051] The number average particle size of the silicone particles (B) may be within a range relatively larger than the number average particle size of the polymer particles (A). The number average particle size of the silicone particles (B) is preferably within a range of 100 nm to 300 nm, and more preferably within a range of 150 nm to 250 nm. When the number average particle size of the silicone particles (B) is within this range, light scattering can be reduced, thereby reducing the haze of the resulting coating film.

[0052] The number average particle size of the silicone particles (B) is the particle size (D50) value at which the cumulative frequency of the number of particles when accumulating particles starting from the smallest particle is 50% when the particle size distribution is measured using a particle size distribution measuring device that uses light scattering as the measurement principle. Examples of such particle size distribution measuring devices include Coulter LS230, LS100, and LS13 320 (all manufactured by Beckman Examples of such a filter include FPAR-1000 (manufactured by Coulter, Inc.) and FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).

[0053] The content of the silicone particles (B) in the composition according to this embodiment is preferably 2 to 60 parts by mass, and more preferably 3 to 50 parts by mass, per 100 parts by mass of the polymer particles (A). By including the silicone particles (B) within this range, the frictional resistance of the coating film surface can be reduced, thereby improving the blocking resistance of the resulting coating film.

[0054] 1.3. Liquid Medium (C) The composition according to this embodiment contains a liquid medium (C). The liquid medium (C) is preferably an aqueous medium containing water. The aqueous medium may contain a non-aqueous medium other than water. Examples of such non-aqueous medium include amide compounds, hydrocarbons, alcohols, ketones, esters, amine compounds, lactones, sulfoxides, and sulfone compounds, and one or more selected from these may be used. When the liquid medium (C) contains water and a non-aqueous medium, it is preferable that the total mass of the liquid medium (C) is 100% by mass, and more preferably 90% by mass or more of the liquid medium (C) 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 increased.

[0055] The content of the non-aqueous medium in the aqueous medium is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably substantially free of the non-aqueous medium, based on 100% by mass of the aqueous medium. Here, "substantially free of the non-aqueous medium" means that the non-aqueous medium is not intentionally added as a liquid medium, and the composition may contain a non-aqueous medium that is inevitably mixed in when preparing the composition.

[0056] 1.4. Other additives The composition according to the present embodiment may contain additives other than the above-mentioned components, such as thickeners, fillers, preservatives, and pH adjusters, as needed.

[0057] <Thickener> Examples of thickeners 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 (co)polymers such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers; and water-soluble polymers such as saponified copolymers of vinyl esters with unsaturated carboxylic acids such as (meth)acrylic acid, maleic acid, and fumaric acid. Among these, alkali metal salts of carboxymethyl cellulose and alkali metal salts of poly(meth)acrylic acid are particularly preferred.

[0058] Commercially available thickeners include alkali metal salts of carboxymethylcellulose such as CMC1120, CMC1150, CMC2200, CMC2280, and CMC2450 (all manufactured by Daicel Corporation).

[0059] When the composition according to this embodiment contains a thickener, the amount of the thickener used is preferably 5% by mass or less, and more preferably 0.1 to 3% by mass, based on the total solid content of the composition.

[0060] <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 in addition, inorganic fillers derived from minerals such as talc and mica, and one or more of these can be used.

[0061] <Preservative> The composition according to this embodiment can suppress the growth of bacteria, molds, etc. and the generation of foreign substances when storing the composition 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., and one or more of these can be used.

[0062] <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, for example, hydrochloric acid, phosphoric acid, sulfuric acid Examples of suitable compounds include acidic compounds such as acetic acid and formic acid; and basic compounds such as potassium hydroxide, ethylenediamine, monoethanolamine, TMAH (tetramethylammonium hydroxide), TEAH (tetraethylammonium hydroxide), and ammonia.

[0063] In the present invention, pH refers to hydrogen ion exponent, and its value can be measured using a commercially available pH meter (for example, a tabletop pH meter manufactured by Horiba, Ltd.) under conditions of 25°C and 1 atmosphere.

[0064] 1.5. Method for producing the composition The composition according to this embodiment may be prepared by mixing the above-mentioned components, and may be prepared, for example, by the method described in JP-A-2007-332202.

[0065] 2. Working Example The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In these examples, "parts" and "%" are by mass unless otherwise specified.

[0066] 2.1. Preparation of dispersion containing polymer particles (A) 2.1.1. Preparation of Dispersion P-1 After thoroughly replacing the inside of a 3 L separable flask with nitrogen, 50.0 parts by mass of ion-exchanged water and 0.3 parts by mass of ammonium persulfate (APS) were added. The internal temperature was adjusted to 80°C while stirring. In a separate container, 60.0 parts by mass of ion-exchanged water, 49.0 parts by mass of methyl methacrylate (MMA), 41.0 parts by mass of butyl acrylate (BA), 10.0 parts by mass of methacrylic acid (MAA), 2.4 parts by mass of emulsifier "Latemul E-118B" (trade name, manufactured by Kao Corporation), and 1.0 part by mass of emulsifier "ADEKA REASOAP SR-1025" (trade name, manufactured by ADEKA Corporation) were mixed and stirred to prepare an emulsion. The resulting emulsion was continuously added dropwise to the reaction vessel over a period of 3 hours. After the dropwise addition, the mixture was stirred at 80° C. for 3 hours and then cooled to 40° C., and 0.1 parts by mass of aqueous ammonia and water were added to obtain a dispersion P-1 containing 45% by mass of polymer particles (A).

[0067] The particle size distribution of the obtained dispersion P-1 was measured using a particle size distribution measuring device (Otsuka Electronics Co., Ltd., model "FPAR-1000") that uses dynamic light scattering as its measurement principle, and the number average particle diameter (D50) was calculated from the particle size distribution, and the number average particle diameter (D50) was found to be 70 nm.

[0068] 2.1.2. Preparation of Dispersions P-2 to P-4 Dispersions P-2, P-3, and P-4 containing 45% by mass of polymer particles (A) were obtained in the same manner as in the above "2.1.1. Preparation of Dispersion P-1," except that the types and amounts of the monomer, polymerization initiator, emulsifier, and neutralizing agent were changed as shown in Table 1 below, and the number average particle diameter (D50) of the polymer particles (A) was determined for each dispersion.

[0069] [Table 1]

[0070] The following products or reagents were used for each component in Table 1 above. <Monomer> MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, product name "Acryester M") BA: Butyl acrylate (manufactured by Mitsubishi Chemical Corporation, product name "Butyl acrylate") EHA: 2-Ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd., product name "2-Ethylhexyl acrylate") MAA: Methacrylic acid (manufactured by Mitsubishi Chemical Corporation, product name "MAA") <Polymerization initiator> APS: Ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc., product name "Ammonium persulfate") <Emulsifier> Latemul E-118B: Polyoxyethylene alkyl ether sodium sulfate (manufactured by Kao Corporation, product name "Latemul E-118B") ADEKA REASOAP SR-1025: ammonium salt of α-sulfo-ω-(1-alkoxy)methyl-2-(2-propenyloxy)ethoxy-poly(oxy-1,2-ethanediyl) (manufactured by ADEKA Corporation, trade name "ADEKA REASOAP SR-1025") Kuraray Poval 5-88: Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., product name "Kuraray Poval 5-88") <Neutralizer> Ammonia water: Manufactured by Taisei Kako Co., Ltd., product name "Ammonia"

[0071] 2.2. Preparation of Dispersion Containing Silicone Particles (B) 2.2.1. Preparation of Dispersion S-1 98.0 parts by mass of decamethylcyclopentasiloxane (DMCPS), 2.0 parts by mass of tetraethoxysilane (TEOS), 2.9 parts by mass of dodecylbenzenesulfonic acid (SDBA), 1.4 parts by mass of sodium dodecylbenzenesulfonate (SDBS), and 178 parts by mass of water were placed in a 500 mL SUS beaker and emulsified by stirring. After that, a uniform emulsion was obtained by treating with an ultrasonic disperser (Hielscher, UP400S) for 4 minutes. This emulsion was transferred to a 500 mL separable flask and subjected to polymerization reaction at 70 ° C for 6 hours. After that, 2 parts by mass of 10% ammonia water and water were added to obtain dispersion S-1 containing 35% by mass of silicone particles (B).

[0072] The particle size distribution of the obtained dispersion S-1 was measured using a particle size distribution measuring device (Otsuka Electronics Co., Ltd., model "FPAR-1000") that uses dynamic light scattering as its measurement principle, and the number average particle diameter (D50) was calculated from the particle size distribution, and the number average particle diameter (D50) was found to be 240 nm.

[0073] 2.2.2. Preparation of Dispersions S-2 and S-3 Dispersions S-2 and S-3 containing 45% by mass of silicone particles (B) were obtained in the same manner as in "2.2.1. Preparation of Dispersion S-1" above, except that the types and amounts of monomer, polymerization initiator, emulsifier, and neutralizing agent were changed as shown in Table 2 below, and the number average particle diameter (D50) of the silicone particles (B) was determined.

[0074] [Table 2]

[0075] The following products or reagents were used for each component in Table 2 above. <Monomer> DMCPS: Decamethylcyclopentasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KF-995") TEOS: Tetraethoxysilane (Tama Chemicals Co., Ltd., product name "TEOS") <Polymerization initiator> SDBA: Dodecylbenzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Dodecylbenzenesulfonic acid") <Emulsifier> SDBS: Sodium dodecylbenzenesulfonate (Kao Corporation, product name "Neopelex G-25") <Neutralizer> Ammonia water: Manufactured by Taisei Kako Co., Ltd., product name "Ammonia"

[0076] 2.3. Examples 1 to 5 and Comparative Examples 1 to 3 2.3.1. Preparation of the Composition The components were mixed to obtain the content ratios shown in Table 3 below, and water was added so that the total amount of polymer particles (A) and silicone particles (B) shown in Table 3 below was 30 mass %, thereby preparing the compositions of each example and comparative example.

[0077] 2.3.2. Evaluation Method 15 g of butyl carbitol was added to 100 g of the composition prepared above, and the mixture was stirred for 2 hours to prepare a composition for evaluation. The obtained composition for evaluation was applied to a glass substrate to a film thickness of 10 μm, and then dried at 80° C. for 5 minutes to prepare a coating film for evaluation. The following evaluations were performed using the prepared coating film for evaluation.

[0078] <Repelling evaluation> When the composition is mixed with other components and then coated, if there is a lot of cissing, it becomes difficult to obtain a uniform coating film, and in some cases the composition cannot be used in practice. For this reason, cissing was evaluated by the following method. (Evaluation method) The coating films for evaluation obtained above were visually evaluated, and the results are shown in Table 3 below. (Evaluation criteria) AA: Since no cissing was observed, there are no restrictions on the ingredients to be mixed when producing the coating film, and the coating can be used in practical applications, so it is judged to be particularly good. A: One or two spots of cissing are observed on the coated surface, but the coating is still suitable for practical use and is therefore judged to be in very good condition. B: Three to five cissing spots were observed on the coating surface, and although care must be taken with the ingredients mixed when creating the coating, it is judged to be good as it may be suitable for practical use. C: Repelling was observed over the entire surface, making it difficult to put the sample to practical use and judged to be poor.

[0079] <Evaluation of blocking resistance> When a coating film is produced by mixing the composition with other components, if the coating film has low blocking resistance, the coated substrates may stick to each other when stacked or wound on a roll, making it impossible to use in practice. For this reason, blocking resistance was evaluated by the following method. (Evaluation method) A glass substrate was placed on the coating film for evaluation obtained above, and the film was left to stand in a dryer at 60°C for 1 hour. The glass substrate was then peeled off, and the coating surface was visually evaluated. The results are shown in Table 3 below. (Evaluation criteria) AA: The glass substrate can be peeled off without any resistance, and no traces are found on the coating surface. The coating is suitable for practical use and is therefore judged to be particularly good. A: Although some resistance is felt when peeling off the glass substrate, no traces are found on the coating surface, and the coating is suitable for practical use and is therefore judged to be very good. B: Some resistance was felt when peeling off the glass substrate, and slight marks were observed on the surface of the coating film. Care must be taken with the ingredients mixed when creating the coating film, but the film is suitable for practical use and is therefore judged to be good. C: Marks are clearly visible on the coating surface, making it difficult to put into practical use and judged to be poor.

[0080] <Hayes' evaluation> When a coating film is prepared by mixing the composition with other components, if the haze of the coating film becomes large, the transparency is impaired and the coating film may become unusable for practical use. For this reason, the haze was evaluated by the following method. (Evaluation method) The haze of the coating film for evaluation obtained above was evaluated using a turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd., model "HAZE METER NDH 5000") The results are also shown in Table 3 below. (Evaluation criteria) AA: The haze is 1 or less, there are no apparent limitations on the components to be mixed when producing the coating film, and the coating can be put to practical use, so it is judged to be particularly good. A: The haze is greater than 1 and less than or equal to 3, and is judged to be very good since it can be used in practical applications. B: The haze is greater than 3 and equal to or less than 5, and although care must be taken with the components mixed when preparing the coating film, it is judged to be good because it can be used in practical applications. C: The haze is more than 5, and it is difficult to put the film to practical use, and the film is judged to be poor.

[0081] <Evaluation of dynamic friction coefficient> When a coating film is produced by mixing the composition with other components, if the coefficient of dynamic friction of the coating film becomes large, the films may be scratched when stacked and stored, causing scratches on the surface, making it unusable for practical use. For this reason, the coefficient of dynamic friction was evaluated using the following method. (Evaluation method) The coefficient of dynamic friction of the coating film for evaluation obtained above was evaluated using a surface property measuring device (manufactured by Shinto Scientific Co., Ltd., model "Tribogear TYPE: 14FW") The results are also shown in Table 3 below. (Evaluation criteria) AA: The coefficient of dynamic friction is 0.4 or less, there are no restrictions on the components to be mixed when producing the coating film, and it can be used in practical applications, so it is judged to be particularly good. A: The coefficient of dynamic friction is greater than 0.4 and equal to or less than 0.6, and is judged to be very good since it can be used in practical applications. B: The coefficient of dynamic friction is greater than 0.6 and equal to or less than 0.8. Although care must be taken with the ingredients mixed when producing the coating film, the coating is judged to be good because it can be used in practice. C: The dynamic friction coefficient is greater than 0.8, making it difficult to put into practical use and judged to be poor.

[0082] 2.4.Evaluation Results Table 3 below shows the compositions used in Examples 1 to 5 and Comparative Examples 1 to 3, as well as the evaluation results.

[0083] [Table 3]

[0084] According to the evaluation results in Table 3 above, the coating films prepared using the compositions according to the present invention shown in Examples 1 to 5 exhibited good effects, such as suppressing cissing, good blocking resistance, excellent haze, and a satisfactory dynamic friction coefficient.

[0085] In contrast, in the compositions shown in Comparative Examples 1 to 3, the number average particle size of the polymer particles (A) is larger than the number average particle size of the silicone particles (B), and as a result, the coating films produced using the compositions shown in Comparative Examples 1 to 3 have high haze, making them difficult to put into practical use.

[0086] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations with the same function, method, and result, or configurations with the same purpose and effect). The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. The present invention also includes configurations that achieve the same effects or purposes as the configurations described in the embodiments. The present invention also includes configurations in which publicly known technology is added to the configurations described in the embodiments.

Claims

1. A composition containing polymer particles (A), silicone particles (B), and a liquid medium (C), the polymer particles (A) have a repeating unit (Ma) derived from methyl (meth)acrylate and a repeating unit (Mb) derived from an unsaturated carboxylic acid, A composition, wherein the number average particle size of the polymer particles (A) is smaller than the number average particle size of the silicone particles (B).

2. The composition according to claim 1 , wherein the silicone particles (B) have repeating units derived from cyclic silicone.

3. 3. The composition according to claim 1, wherein the number average particle diameter of the polymer particles (A) is 30 nm to 600 nm.

4. 3. The composition according to claim 1, wherein the silicone particles (B) are contained in an amount of 2 to 60 parts by mass per 100 parts by mass of the polymer particles (A).

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