Emulsion composition and production method therefor

Abstract

The purpose of the present invention is to provide: an emulsion composition which is an easily formable emulsion including a polymer containing a hydrolyzable silyl group; and a method for producing the emulsion composition. The emulsion composition comprises (A) a polyoxyalkylene-based polymer (A1) containing a hydrolyzable silyl group and / or a (meth)acrylic-ester-based copolymer (A2) containing a hydrolyzable silyl group, (B) water, and (C) a lamellar filler, wherein the (C) component is contained in an amount of 1.5-20 parts by weight per 100 parts by weight of the sum of the (A) and (B) components.

Description

Emulsion composition and method for producing same

[0001] The present invention relates to an emulsion composition containing a hydrolyzable silyl group-containing polymer and a method for producing the same.

[0002] As an emulsification technique for a hydrolyzable silyl group-containing polymer, for example, Patent Document 1 discloses a silylated polymer emulsion containing a silylated polymer, water, nanosilica, and an optional emulsifier.

[0003] Furthermore, Patent Document 2 discloses a reactive emulsion in which a polyether or polyester having at least one reactive silicon group in a side chain or at a terminal per molecule is dispersed in water using a surfactant.

[0004] JP 2009-520867 A

[0005] However, the conventional techniques described in Patent Documents 1 and 2, etc., require high-speed dispersion, and there is room for improvement from the viewpoint of simplifying the manufacturing process.

[0006] Therefore, an object of the present invention is to provide an emulsion composition that can easily form an emulsion containing a hydrolyzable silyl group-containing polymer, and a method for producing the same.

[0007] As a result of extensive research into means capable of solving the above problems, the present inventors have found for the first time that an emulsion composition capable of easily forming an emulsion containing a hydrolyzable silyl group-containing polymer can be obtained by adding a layered filler to an emulsion composition containing a specific hydrolyzable silyl group-containing polymer, and have thus completed the present invention.

[0008] Therefore, one aspect of the present invention is an emulsion composition (hereinafter referred to as "the present emulsion composition") comprising (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water, and (C) a layered filler, wherein the amount of the component (C) is 1.5 to 20 parts by weight per 100 parts by weight of the total of the components (A) and (B).

[0009] Another aspect of the present invention is a method for producing an emulsion composition (hereinafter referred to as "the present production method"), comprising a stirring step of mixing and stirring (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water, and (C) a layered filler in an amount of 1.5 to 20 parts by weight of the component (C) per 100 parts by weight of the total of the components (A) and (B).

[0010] According to one aspect of the present invention, it is possible to provide an emulsion composition that can easily form an emulsion containing a hydrolyzable silyl group-containing polymer.

[0011] An embodiment of the present invention will be described in detail below. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more, B or less." In addition, all documents described in this specification are incorporated herein by reference.

[0012] 1. Overview of the Invention Conventionally, as a technique for emulsifying a hydrolyzable silyl group-containing polymer, a technique for emulsifying a hydrolyzable silyl group-containing polymer by mixing the polymer, a surfactant, and water is known (for example, Patent Documents 1 and 2).

[0013] In the course of investigations by the present inventors, it was thought that it would be difficult to produce an aqueous emulsion containing a hydrolyzable silyl group-containing polymer, since the presence of water could cause a condensation reaction of the hydrolyzable silyl groups in the hydrolyzable silyl group-containing polymer to proceed.

[0014] Therefore, the present inventors have conducted extensive research into means capable of solving the above problems, and as a result have succeeded in discovering that an emulsion containing a hydrolyzable silyl group-containing polymer can be easily formed by adding a layered filler when producing an aqueous emulsion containing a specific hydrolyzable silyl group-containing polymer.

[0015] Such a technique for easily producing an emulsion containing a hydrolyzable silyl group-containing polymer has not been known before, and is extremely useful in fields where emulsions containing hydrolyzable silyl group-containing polymers are used.

[0016] As described above, according to the configuration of one aspect of the present invention, an aqueous emulsion containing a hydrolyzable silyl group-containing polymer can be easily obtained, which can contribute to the achievement of Sustainable Development Goals (SDGs) such as Goal 12 "Ensure sustainable consumption and production patterns" and Goal 11 "Make cities and towns inclusive and sustainable" The configuration of this emulsion composition is described in detail below.

[0017] [2. Emulsion Composition] As described above, the present emulsion composition contains (A) at least one of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water, and (C) a layered filler.

[0018] In the following, the "hydrolyzable silyl group-containing polyoxyalkylene polymer (A1)" may be referred to as the "(A1) component," the "hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2)" may be referred to as the "(A2) component," the "(B) water" may be referred to as the "(B) component," and the "(C) layered filler" may be referred to as the "(C) component." Furthermore, the "(A) hydrolyzable silyl group-containing polyoxyalkylene polymer (A1)" and the "hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2)" may be collectively referred to as the "(A) component."

[0019] (2-1. Component (A)) The present emulsion composition contains, as component (A), at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2).

[0020] In one embodiment of the present invention, the component (A) may be a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1), a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), or a combination of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2).

[0021] <Hydrolyzable Silyl Group-Containing Polyoxyalkylene Polymer (A1)> The hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) is a compound in which the polymer portion (also referred to as the "main chain") of a hydrolyzable silyl group-containing polymer is a polyoxyalkylene compound. The hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) forms intermolecular siloxane bonds to form a crosslinked product under specific conditions known to those skilled in the art.

[0022] In one embodiment of the present invention, the lower limit of the number average molecular weight (Mn) of component (A) is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and most preferably 10,000 or more. The upper limit of the number average molecular weight of component (A) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. If the number average molecular weight is within the above range, it is easy to prepare an aqueous dispersion of the polymer.

[0023] In one embodiment of the present invention, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of component (A) (Mw / Mn; molecular weight distribution) is preferably 1.6 or less, more preferably 1.5 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and especially preferably 1.2 or less. When the molecular weight distribution is within the above range, the polymer has a low viscosity, making it easy to prepare an aqueous dispersion of the polymer.

[0024] In the present specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0025] The molecular weight of component (A) can also be expressed as an end-group-converted molecular weight, which is calculated by directly measuring the end-group concentration of a polymer precursor before the introduction of hydrolyzable silyl groups by titration analysis based on the principles of the hydroxyl value measurement method specified in JIS K 1557 and the iodine value measurement method specified in JIS K 0070, and taking into account the polymer structure (the degree of branching determined by the polymerization initiator used). The end-group-converted molecular weight of polymer (A) can also be calculated by preparing a calibration curve of the number average molecular weight (Mn) determined by general GPC measurement of the polymer precursor and the end-group-converted molecular weight, and converting the number average molecular weight (Mn) determined by GPC of the hydrolyzable silyl group-containing polymer into an end-group-converted molecular weight.

[0026] [Hydrolyzable Silyl Group] The structure of the hydrolyzable silyl group contained in component (A1) is not particularly limited, and any hydrolyzable silyl group commonly used in this technical field may be used.

[0027] In one embodiment of the present invention, the hydrolyzable silyl group of the component (A1) is represented by the following general formula (1). Two or more types of hydrolyzable silyl groups represented by general formula (1) may be contained in one polymer molecule. １ ) ３－ａ (X) ａ (1) In the formula, R １ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group). １ When there are two or more R １ The structures of R may be the same or different. １ Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0028] X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, alkoxy groups such as a methoxy group and an ethoxy group are more preferred, a methoxy group and an ethoxy group are even more preferred, and a methoxy group is particularly preferred, because they are mildly hydrolyzable and easy to handle.

[0029] a is 1, 2 or 3. a is preferably 2 or 3, which forms a network structure by condensation to give a cured product.

[0030] Generally, the fewer the carbon atoms in an alkoxy group, the more reactive it is. That is, the reactivity decreases in the order of methoxy, ethoxy, and propoxy. This property can be utilized to appropriately determine the specific structure of the hydrolyzable silyl group depending on the production method and intended use of component (A1).

[0031] Specific examples of the hydrolyzable silyl group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a (chloromethyl)dimethoxysilyl group, and a (methoxymethyl)dimethoxysilyl group.

[0032] Considering the physical properties of the resulting cured product and the ease of obtaining and handling the raw material compounds, the hydrolyzable silyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group. Furthermore, considering the fast crosslinking reaction rate, a trialkoxysilyl group is preferred. Among the specific examples mentioned above, one or more selected from a trimethoxysilyl group, a triethoxysilyl group, and a triisopropoxysilyl group are preferred, with a trimethoxysilyl group being more preferred.

[0033] The lower limit of the number of hydrolyzable silyl groups contained in one polymer molecule is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. The upper limit of the number of hydrolyzable silyl groups contained in one polymer molecule is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. If the number of hydrolyzable silyl groups is within the above range, sufficient flexibility can be imparted to the cured product obtained by the condensation reaction of the silyl groups.

[0034] The distribution of hydrolyzable silyl groups may be random or block-like. The distribution position of the hydrolyzable silyl groups may be anywhere on the polymer molecule. Preferably, the distribution positions of the hydrolyzable silyl groups include the terminals or near-terminals of the polymer molecule. More preferably, the distribution positions of the hydrolyzable silyl groups are localized at the terminals or near-terminals of the polymer molecule. In one embodiment of the present invention, "near the terminals of the polymer molecule" refers to the region from each terminal of the polymer molecule to position P in the polymer molecule, and the weight of this region accounts for 20 wt% or less, 15 wt% or less, or 10 wt% or less of the total weight of the polymer molecule. In one embodiment of the present invention, "localized at the terminals or near-terminals of the polymer molecule" means that the number of hydrolyzable silyl groups located at the terminals or near-terminals of the polymer molecule accounts for 70% or more, 80% or more, or 90% or more.

[0035] A known method may be used to introduce a hydrolyzable silyl group into a polyoxyalkylene polymer.

[0036] [Polyoxyalkylene] The polyoxyalkylene structure in component (A1) may be linear or branched. Preferably, the polyoxyalkylene structure is a structure derived from polyoxypropylene diol or polyoxypropylene triol.

[0037] The polyoxyalkylene polymer molecule may be composed of only one type of repeating unit or may contain two or more types of repeating units.One type of polyoxyalkylene polymer may be blended, or two or more types of polyoxyalkylene polymers may be blended.

[0038] An example of the main chain structure of the polyoxyalkylene polymer is a structure having a repeating unit represented by the following general formula (3): ２ is a divalent alkylene group. ２ The structure represented by general formula (2) preferably accounts for 50% by weight or more of the total weight of the polyoxyalkylene polymer in component (A1), more preferably 70% by weight or more, and even more preferably 90% by weight or more.

[0039] R contained in general formula (2) ２ The specific structure of R is not particularly limited. ２ is preferably an alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.

[0040] Specific examples of the repeating unit represented by formula (2) include: ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O—, —CH ２ CH(C ２ H ５ ) O—, —CH ２ C(CH ３ ) ２ O-, -CH ２ CH ２ CH ２ CH ２ Among these, —CH ２ CH (CH ３ )O— is preferred. ２ CH (CH ３ Polyoxyalkylene polymers containing )O- in the repeating unit can easily adjust the glass transition temperature (Tg) to 0°C or lower.

[0041] The polyoxyalkylene polymer may contain a urethane bond or a urea bond in the main chain structure.

[0042] Commercially available polyoxyalkylene polymers can also be used, including Kaneka MS Polymer (registered trademark) S810, S257, S327, S203H, and S303H (all manufactured by Kaneka Corporation); Silyl (registered trademark) SAX220, SAT350, SAT400, SAX510, SAX520, SAX580, SAX590, and SAX750 (all manufactured by Kaneka Corporation); Exestar (registered trademark) ES-S2410, ES-S2420, and ES-S3630 (all manufactured by AGC Inc.); and GENIOSIL (registered trademark) STP-E10, STP-E15, STP-E-30, and STP-E-35 (all manufactured by Wacker).

[0043] (Method for Producing Polyoxyalkylene Polymer) The following methods (I) to (III) can be used to produce the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1).

[0044] (I) A method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with a hydroxyl group-containing initiator using a composite metal cyanide complex catalyst, and then the hydroxyl groups of the obtained hydroxyl-terminated polyoxyalkylene polymer are converted to carbon-carbon unsaturated groups, and then a silane compound is added by a hydrosilylation reaction.

[0045] (II) A method in which a hydroxyl-terminated polyoxyalkylene polymer is obtained by polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst, and then the obtained hydroxyl-terminated polyoxyalkylene polymer is reacted with a compound having both a group reactive with a hydroxyl group and a hydrolyzable silyl group.

[0046] (III) A method in which a hydroxyl-terminated polyoxyalkylene polymer is reacted with an excess of a polyisocyanate compound to form a polymer having an isocyanate group at its terminal, and then a compound having both a group reactive with an isocyanate group and a hydrolyzable silyl group is reacted with the polymer.

[0047] Examples of initiators having a hydroxyl group to be used in methods (I) and (II) include those having one or more hydroxyl groups, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low-molecular-weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, methanol, ethanol, propanol, butanol, pentanol, hexanol, polypropylene monoallyl ether, and polypropylene monoalkyl ether.

[0048] Examples of epoxy compounds used in methods (I) and (II) include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether, etc. Among these, propylene oxide is preferred.

[0049] Examples of the carbon-carbon unsaturated group used in method (I) include a vinyl group, an allyl group, a methallyl group, a propargyl group, etc. Among these, an allyl group is preferred.

[0050] As a method for converting the hydroxyl groups of (I) into carbon-carbon unsaturated groups, a method of reacting an alkali metal salt with a hydroxyl-terminated polymer and then reacting it with a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferably used.

[0051] Examples of the halogenated hydrocarbon compound used in method (I) include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, vinyl iodide, allyl iodide, methallyl iodide, and propargyl iodide.

[0052] Examples of the hydrosilane compound that can be used in method (I) include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, (chloromethyl)dimethoxysilane, (methoxymethyl)dimethoxysilane, and (N,N-diethylaminomethyl)dimethoxysilane.

[0053] The hydrosilylation reaction used in method (I) is accelerated by various catalysts. Known catalysts may be used as the hydrosilylation catalyst. Examples include platinum supported on a support such as alumina, silica, or carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, or ketones; platinum-olefin complexes [e.g., Pt(CH ２ =CH ２ ) ２ (PPh ３ ), Pt(CH ２ =CH ２ ) ２ Cl ２ ]; platinum-vinylsiloxane complex [Pt{(vinyl)Me ２ SiOSiMe ２ (vinyl)}, Pt{Me(vinyl)SiO} ４ ]; platinum-phosphine complex [Ph(PPh ３ ) ４ , Pt(PBu ３ ) ４ ]; platinum-phosphite complex [Pt{P(OPh) ３} ４ ] etc. can be used.

[0054] Examples of compounds having both a group reactive with a hydroxyl group and a hydrolyzable silyl group that can be used in method (II) include isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, and isocyanatemethyldimethoxymethylsilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyltriethoxysilane; and epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropyltriethoxysilane.

[0055] Examples of polyisocyanate compounds that can be used in method (III) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; and aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.

[0056] Compounds having both a group reactive with an isocyanate group and a hydrolyzable silyl group that can be used in the method (III) include γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-(N-phenyl)aminopropyltrimethoxysilane, γ-(N-phenyl)aminopropyltriethoxysilane, Examples thereof include amino group-containing silanes such as propyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane, N-ethylaminoisobutyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, and N-cyclohexylaminomethyldimethoxymethylsilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyldimethoxymethylsilane; and mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxymethylsilane.

[0057] Furthermore, a polyoxyalkylene polymer having multiple hydrolyzable silyl groups at one terminal can also be used as the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1). A polyoxyalkylene polymer having multiple hydrolyzable silyl groups at one terminal can be synthesized by (i) using a double metal cyanide complex catalyst to polymerize an epoxy compound with a hydroxyl group-containing initiator to obtain a hydroxyl-terminated polyoxyalkylene polymer, (ii) reacting an alkali metal salt with the hydroxyl groups of the obtained hydroxyl-terminated polyoxyalkylene polymer with allyl glycidyl ether, further reacting an alkali metal salt with the resulting hydroxyl terminal, and then reacting a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond to obtain a polyoxyalkylene polymer having multiple carbon-carbon unsaturated groups at one terminal, or (iii) adding a silane compound to the obtained polyoxyalkylene polymer having multiple carbon-carbon unsaturated groups at one terminal by hydrosilylation.

[0058] <Hydrolyzable Silyl Group-Containing (Meth)acrylic Acid Ester Copolymer (A2)> The hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) is a compound in which the polymer portion of a hydrolyzable silyl group-containing polymer is a (meth)acrylic acid ester copolymer. The hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) forms intermolecular siloxane bonds to form a crosslinked product under specific conditions known to those skilled in the art.

[0059] [Hydrolyzable Silyl Group] For the hydrolyzable silyl group in the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), the description in the section [Hydrolyzable Silyl Group] of <Hydrolyzable Silyl Group-Containing Polyoxyalkylene Polymer (A1)> above is incorporated by reference.

[0060] [(Meth)acrylic acid ester] The (meth)acrylic acid ester contains a structural unit derived from a (meth)acrylic monomer. In this specification, "(meth)acrylic" refers to acrylic and / or methacrylic.

[0061] The (meth)acrylic acid ester structure in the component (A2) may be linear or branched.

[0062] The (meth)acrylic acid ester molecule may be composed of only one type of repeating unit, or may contain two or more types of repeating units. One type of (meth)acrylic acid ester may be blended, or two or more types of (meth)acrylic acid esters may be blended.

[0063] An example of the (meth)acrylic acid ester structure is a structure represented by the following general formula (3): ３ is a hydrogen atom or a methyl group, and R ４ is a group having one or more carbon atoms. ４ The number of carbon atoms in R may be, for example, 1 to 22. ４ R can be an alkyl group, a cycloalkyl group, or an aryl group. ４ may be substituted with a halogen, a hydroxy group, an alkoxy group, an amino group, etc. ３ )-CH(COOR ４)-(3) The structure represented by general formula (3) is obtained by polymerization of a (meth)acrylic monomer. Specific examples of the (meth)acrylic monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and methyl (meth)acrylate. 2-Ethylhexyl, octyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isopropoxyethyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,2,2-Trifluoroethyl, glycidyl (meth)acrylate, 1-ethylcyclopentyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, icosyl (meth)acrylate, docosyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate, isobornyl (meth)acrylate, 2-aminoethyl (meth)acrylate Examples of suitable acrylates include methyl acrylate, γ-(methacryloyloxypropyl)trimethoxysilane, ethylene oxide adducts of (meth)acrylic acid, trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethylmethyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

[0064] Among the above-mentioned (meth)acrylic monomers, one or more selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and stearyl acrylate are preferred. A main chain structure formed from these monomers can easily adjust the glass transition temperature (Tg) to 0°C or lower.

[0065] Commercially available (meth)acrylic acid esters may also be used. Examples of commercially available products include XMAP (registered trademark) SA100S, SA110S, SA120S, SA310S, and SA410S (all manufactured by Kaneka Corporation); ARUFON (registered trademark) US-6100, US-6110, US-6120, US-6130, US-6140, US-6150, US-6170, US-6180, and US-6190 (all manufactured by Toagosei Co., Ltd.); Actflow NE-1000 (registered trademark) (manufactured by Soken Chemical & Engineering Co., Ltd.); and Joncryl (registered trademark) (manufactured by BASF).

[0066] In one embodiment of the present invention, the (meth)acrylic acid ester preferably contains an XY diblock structure or an XYX triblock structure in the molecule. Here, the X block is a block having a relatively high content of hydrolyzable silyl groups. The Y block is a Y block having a relatively low content of hydrolyzable silyl groups. The overall molecular structure of the (meth)acrylic acid ester is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure. Here, the "XYX triblock structure" refers to the "ABA triblock structure" commonly referred to by those skilled in the art.

[0067] The number of repeating units derived from the hydrolyzable silyl group-containing monomer contained in the X block is on average more than 1.0, preferably 1.5 or more, and more preferably 1.7 or more, and the number of repeating units derived from the hydrolyzable silyl group-containing monomer contained in the X block is preferably more than 3 wt %, more preferably 4.5 wt % or more, and even more preferably 5 wt % or more, based on the weight of all repeating units contained in the X block.

[0068] In one embodiment of the present invention, the (meth)acrylic acid ester is an XYX triblock polymer, and each of the blocks (X blocks) constituting the terminal portions of the (meth)acrylic acid ester preferably has more than one hydrolyzable silyl group.

[0069] The repeating units derived from the hydrolyzable silyl group-containing monomer contained in the Y block are contained in an amount of 0 to 3 wt %, preferably 0 to 2 wt %, and more preferably 0 to 1 wt %, based on the weight of all repeating units contained in the Y block.

[0070] In a (meth)acrylic acid ester having an XY diblock structure or an XYX triblock structure in the molecule, the repeating unit derived from a hydrolyzable silyl group-containing monomer is localized in a region near the terminal (near one or both ends).

[0071] (Method for Producing (Meth)acrylic Acid Ester) The (meth)acrylic acid ester can be produced by a known polymerization method (radical polymerization method, cationic polymerization method, anionic polymerization method, etc.).

[0072] As a preferred method for producing the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), the following methods (i) to (iii) can be used.

[0073] (i) A method in which a compound having a polymerizable unsaturated group and a hydrolyzable silyl group is copolymerized with a monomer having a (meth)acrylic structure.

[0074] (ii) A method in which a monomer having a (meth)acrylic structure is copolymerized in the presence of a compound having a hydrolyzable silyl group and a mercapto group as a chain transfer agent.

[0075] (iii) A method in which a monomer having a (meth)acrylic structure is polymerized by living radical polymerization, and then a hydrolyzable silyl group is introduced into the molecular chain terminal.

[0076] The living polymerization method (iii) is preferred because it allows the introduction of functional groups at the ends of polymer molecules and the synthesis of (meth)acrylic acid esters with narrow molecular weight distributions.

[0077] Examples of the compound having a polymerizable unsaturated group and a hydrolyzable silyl group used in (i) include 3-(dimethoxymethylsilyl)propyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (diethoxymethylsilyl)methyl (meth)acrylate, and 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate.

[0078] Examples of the compound having a hydrolyzable silyl group and a mercapto group used in (ii) include 3-mercaptopropyldimethoxymethylsilane and (mercaptomethyl)dimethoxymethylsilane.

[0079] Examples of the living polymerization method (iii) include a living radical polymerization method, a living cationic polymerization method, and a living anionic polymerization method, and among these, the living radical polymerization method is suitable for producing a (meth)acrylic acid ester. Examples of the living radical polymerization method include the following. Atom Transfer Radical Polymerization (ATRP) (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721) Single Electron Transfer Polymerization (SET-LRP) (see J. Am. Chem. Soc. 2006, 128, 14156; JPSChem 2007, 45, 1607) Reversible Chain Transfer Catalyzed Polymerization (RTCP) (see "Living Radical Polymerization Controlled by Organic Catalysts", Polymer Research Journal, 68, 223-231 (2011); JP2014-111798) Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) Nitroxy radical method (NMP method) Polymerization method using an organotellurium compound (TERP method) Polymerization method using an organoantimony compound (SBRP method) Polymerization method using an organobismuth compound (BIRP method) Iodine transfer polymerization Methods for introducing a hydrolyzable silyl group into a (meth)acrylic acid ester include the method described in JP 2007-302749 A and the method described in JP 2018-162394 A. The method described in JP 2007-302749 A introduces a hydrolyzable silyl group by converting the functional group at the terminal of the (meth)acrylic acid ester. Specifically, the hydrolyzable silyl group is introduced by converting the molecular terminal of the (meth)acrylic acid ester to a hydroxyl group, an alkenyl group, and a hydrolyzable silyl group, in that order. The method described in JP 2018-162394 A introduces a hydrolyzable silyl group by copolymerization with a hydrolyzable silyl group-containing (meth)acrylic acid ester monomer.Specifically, the amount of hydrolyzable silyl group-containing (meth)acrylic acid ester monomer added is controlled depending on the stage of progress of living polymerization, thereby introducing a hydrolyzable silyl group near the terminal of the (meth)acrylic acid ester molecule. The hydrolyzable silyl group-containing (meth)acrylic acid ester obtained by these methods has a hydrolyzable silyl group locally at or near the terminal of the molecule.

[0080] The upper limit of the glass transition temperature (Tg) of the (meth)acrylic acid ester in component (A2) is preferably 100° C. or lower, more preferably 50° C. or lower, even more preferably 0° C. or lower, and most preferably −10° C. or lower. There are no particular restrictions on the lower limit of the glass transition temperature (Tg) of the (meth)acrylic acid ester, but it is preferably −80° C. or higher, more preferably −70° C. or higher. The glass transition temperature of the (meth)acrylic acid ester can essentially be regarded as the glass transition temperature of component (A2) itself.

[0081] (2-2. Component (B)) The present emulsion composition contains water as component (B). Water functions as a solvent in cooperation with component (C) to dissolve component (A) and form an emulsion.

[0082] In the present emulsion composition, the weight ratio of the component (A) to the component (B) is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and even more preferably 60:40 to 40:60. When the weight ratio of the component (A) to the component (B) in the present emulsion composition is 20:80 to 80:20, the obtained emulsion has a stable effect.

[0083] (2-3. Component (C)) The present emulsion composition contains a layered filler as component (C). By including component (C) in the present emulsion composition, it becomes possible to form a stable emulsion of the hydrolyzable silyl group-containing polymer and water, and it is possible to easily form an emulsion containing the hydrolyzable silyl group-containing polymer.

[0084] The layered filler is not particularly limited as long as it exhibits the effects of the present invention, but examples include phyllosilicate minerals (also called "layered silicates"), vermiculite, halloysite, swellable mica, graphite, etc., which are composed of multiple two-dimensionally extending layers. From the viewpoint of emulsion stability, layered silicates are preferred. The layered fillers may be used alone or in combination of two or more.

[0085] For forming an emulsion composition, a hydrophilic layered filler is preferred.

[0086] Examples of layered silicates include smectite, etc. Smectite is a montmorillonite group mineral, and examples thereof include montmorillonite (montmorillonite), magnesian montmorillonite, tetromycin montmorillonite, tetromycin magnesian montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite (saponite), aluminian saponite, hectorite, sauconite, stevensite, and bentonite.

[0087] The layered filler may be, for example, a commercially available product. Examples of commercially available layered fillers include natural layered fillers such as the Kunipia series (montmorillonite, e.g., Kunipia-G4, manufactured by Kunimine Industries Co., Ltd.), the Bengel series (bentonite, manufactured by Hojun Co., Ltd.), and the Somasif ME series (swellable mica, manufactured by Co-op Chemical Co., Ltd.). Examples of synthetic layered fillers include Sumecton (saponite, e.g., Sumecton SWF, Sumecton SWN, manufactured by Kunimine Industries Co., Ltd.), Kunigel MB (manufactured by Kunimine Industries Co., Ltd.), and the Lucentite SWN series (hectorite, manufactured by Co-op Chemical Co., Ltd.).

[0088] The size of the layered filler is, for example, 100 nm or more, preferably 150 nm or more, and more preferably 200 nm or more, in terms of primary particle diameter. The upper limit of the size of the layered filler is, for example, 20 μm or less, preferably 15 μm or less, in terms of primary particle diameter. When the size of the layered filler is in the range of 100 nm or more and 20 μm or less, the condensation reaction of the hydrolyzable silyl groups in the hydrolyzable silyl group-containing polymer due to the presence of moisture can be more effectively delayed.

[0089] The content of component (C) in the present emulsion composition is 1.5 to 20 parts by weight, preferably 1.6 to 19 parts by weight, more preferably 1.7 to 18 parts by weight, and even more preferably 1.8 to 17 parts by weight, per 100 parts by weight of the total of component (A) and component (B). When the content of component (C) in the present emulsion composition is 1.5 to 20 parts by weight, a uniform emulsion can be obtained. However, if the content of component (C) is too high (more than 20 parts by weight), stirring becomes difficult, and the emulsion composition may not be easily obtained.

[0090] (2-4. Other Components) The emulsion composition may contain other components than those described above, as appropriate, depending on the intended purpose. Examples of such components include a condensation catalyst that cures the component (A), a filler other than the component (C), an antioxidant, a light stabilizer, an ultraviolet absorber, a water-soluble resin, a solvent, a plasticizer, an antifoaming agent, a leveling agent, a dispersant, a film-forming aid, a coupling agent, a colorant, a water-resistant agent, a cold-resistant agent, a waterproofing agent, a rust inhibitor, a setting regulator, a lubricant, a pH adjuster, a preservative, an inorganic pigment, an organic pigment, a surfactant, a crosslinking agent, an epoxy compound, a polyvalent metal compound, an isocyanate compound, glass fiber, and chemical fiber.

[0091] [3. Method for Producing Emulsion Composition] In one embodiment of the present invention, there is provided a method for producing an emulsion composition, comprising a stirring step of mixing and stirring (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water, and (C) a layered filler, in an amount of 1.5 to 20 parts by weight of component (C) per 100 parts by weight of the total of components (A) and (B). By including the layered filler (C), this production method makes it possible to easily produce an emulsion composition capable of forming an emulsion containing a hydrolyzable silyl group-containing polymer.

[0092] When the other components are added to the present emulsion composition, they may be added and mixed simultaneously with components (A), (B), and (C), or they may be mixed after components (A), (B), and (C) are mixed to form an emulsion.

[0093] In this production method, the method for mixing and stirring component (A), component (B), and component (C) is not particularly limited, and can be any method used in the art. For example, as described in the examples, component (A), component (B), and component (C) can be mixed and stirred simultaneously, or any two components can be mixed and stirred first, and then the remaining component can be added and mixed and stirred. The device for mixing and stirring is also not particularly limited, and for example, a mixer, mechanical stirrer, homogenizer, ultrasonic homogenizer, etc. can be used.

[0094] In one embodiment of the present invention, in the stirring step, the rotation speed of the stirrer is preferably 200 to 1800 rpm, more preferably 250 to 1600 rpm, and even more preferably 300 to 1400 rpm. This production method can produce an emulsion composition that can form an emulsion containing a hydrolyzable silyl group-containing polymer while maintaining a low rotation speed (without requiring high-speed dispersion) compared to conventional techniques.

[0095] In one embodiment of the present invention, the stirring time in the stirring step is preferably 1 to 60 minutes, more preferably 2 to 50 minutes, and even more preferably 3 to 40 minutes. This production method makes it possible to produce an emulsion composition capable of forming an emulsion containing a hydrolyzable silyl group-containing polymer with a shorter stirring time than conventional techniques.

[0096] In one embodiment of the present invention, the stirring temperature in the stirring step is preferably 5 to 80° C., more preferably 10 to 60° C., and even more preferably 15 to 50° C. In this production method, an emulsion composition capable of forming an emulsion containing a hydrolyzable silyl group-containing polymer can be produced at a lower stirring temperature than in conventional techniques.

[0097] In this production method, the "component (A)," "component (B)," and "component (C)" are defined by reference to the contents of the above section [2. Emulsion composition].

[0098] 4. Uses of the Emulsion Composition The emulsion of the present invention can be used, for example, in paints, inks, release agents, adhesives, pressure-sensitive adhesives, sealants, coating materials, cosmetics, and the like.

[0099] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention.

[0100] That is, one aspect of the present invention includes the following. <1> An emulsion composition comprising: (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2); (B) water; and (C) a layered filler, wherein the component (C) is contained in an amount of 1.5 to 20 parts by weight per 100 parts by weight of the total of the components (A) and (B). <2> The emulsion composition according to <1>, wherein the component (C) is a layered silicate. <3> The emulsion composition according to <1> or <2>, wherein the weight ratio of the component (A) to the component (B) is 20:80 to 80:20. <4> The emulsion composition according to any one of <1> to <3>, wherein the component (A) is the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1). <5> A method for producing an emulsion composition, comprising a stirring step of mixing and stirring (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water, and (C) a layered filler, in an amount of 1.5 to 20 parts by weight of the component (C) per 100 parts by weight of the total of the components (A) and (B). <6> A method for producing an emulsion composition according to <5>, wherein, in the stirring step, the rotation speed of the stirrer is 200 to 1800 rpm and the stirring time is 1 to 60 minutes. <7> A method for producing an emulsion composition according to <5> or <6>, wherein, in the stirring step, the stirring temperature is 5 to 80°C. <8> A method for producing an emulsion composition according to any one of <5> to <7>, wherein the component (C) is a layered silicate. <9> The method for producing an emulsion composition according to any one of <5> to <8>, wherein the weight ratio of the component (A) to the component (B) is 20:80 to 80:20. <10> The method for producing an emulsion composition according to any one of <5> to <9>, wherein the component (A) is a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1).

[0101] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0102] [Materials] The materials used in the examples and comparative examples are as follows.

[0103] <Component (A)> A hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) (Synthesis Examples (A-1) to (A-5)) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) (Synthesis Example (A-6)), which were produced based on the following Synthesis Examples, were used.

[0104] <Component (B)> Water <Component (C)> Sumecton SWF (manufactured by Kunimine Industries Co., Ltd., layered silicate, primary particle diameter: 100-1000 nm) Sumecton SWN (manufactured by Kunimine Industries Co., Ltd., layered silicate, primary particle diameter: 100-1000 nm) Kunipia-G4 (manufactured by Kunimine Industries Co., Ltd., layered silicate, primary particle diameter: 100-1000 nm) Kunigel MB (manufactured by Kunimine Industries Co., Ltd., layered silicate, primary particle diameter: 100-1000 nm) <Other fillers> FTL-100 (manufactured by Ishihara Sangyo Kaisha, Ltd., acicular titanium oxide, primary particle diameter: major axis 1.7 μm, minor axis 0.1 μm) Whiscal A (manufactured by Maruo Calcium Co., Ltd., acicular calcium carbonate, primary particle diameter: major axis 20-30 μm, minor axis 0.5-1.0 μm) [Measurement and Evaluation Methods] Measurements and evaluations in the examples and comparative examples were carried out by the following methods.

[0105] (Number Average Molecular Weight) The number average molecular weight in the examples (Synthesis Examples) is a GPC molecular weight measured under the following conditions: Solution delivery system: HLC-8220GPC manufactured by Tosoh Corporation Column: TSKgel Super H series manufactured by Tosoh Corporation Solvent: THF Molecular weight: polystyrene equivalent Measurement temperature: 40°C.

[0106] The average number of hydrolyzable silyl groups per terminal structure and the average number of hydrolyzable silyl groups per molecule of the polymers shown in the Examples (Synthesis Examples) were calculated from the polymer structure and the results of NMR measurement. The molecular weight per silyl group was calculated from the GPC molecular weight and the average number of hydrolyzable silyl groups per molecule.

[0107] (Emulsified State) The mixtures obtained in the examples and comparative examples described below were visually inspected. A mark of ◯ was given when the mixture was uniformly emulsified, and a mark of × was given when the mixture was not emulsified and separated.

[0108] Synthesis Example 1 A synthesis example of polymer (A-1) is shown below.

[0109] Using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene having a number-average molecular weight of 16,400 and a molecular weight distribution Mw / Mn = 1.31 and terminal hydroxyl groups. A 28% methanol solution of 1.2 molar equivalents of sodium methoxide was added to the hydroxyl groups of the resulting hydroxyl-terminated polyoxypropylene. After distilling off the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene to convert the terminal hydroxyl groups to allyl groups, and unreacted allyl chloride was removed by vacuum devolatilization. The resulting unpurified polyoxypropylene was mixed and stirred with n-hexane and water, after which the water was removed by centrifugation. The metal salts in the polymer were removed by vacuum devolatilization of the hexane from the resulting hexane solution. This yielded polyoxypropylene having terminal allyl groups. To 500 g of this polymer, 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt % isopropanol solution calculated as platinum) was added, and 10.9 g of trimethoxysilane was slowly added dropwise while stirring. After reacting at 100°C for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-1) having terminal trimethoxysilyl groups and a number-average molecular weight of approximately 16,400. It was found that polymer (A-1) had an average of 0.7 trimethoxysilyl groups at each terminal and an average of 2.2 trimethoxysilyl groups per molecule.

[0110] [Synthesis Example 2] A synthesis example of polymer (A-2) is shown below.

[0111] Using polyoxypropylene triol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene with a number-average molecular weight of 24,600 and a molecular weight distribution Mw / Mn = 1.31. To the hydroxyl groups of the resulting hydroxyl-terminated polyoxypropylene, 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, 1.5 molar equivalents of allyl chloride were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed and stirred with n-hexane and water, and the water was removed by centrifugation. The metal salts in the polymer were removed by devolatilizing the hexane from the resulting hexane solution under reduced pressure. This resulted in a polyoxypropylene having allyl groups at its ends. To 500 g of this polymer, 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt % isopropanol solution calculated as platinum) was added, and 6.9 g of trimethoxysilane was slowly added dropwise while stirring. The resulting mixture was reacted at 90°C for 2 hours, and then unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (A-2) having trimethoxysilyl groups and a number-average molecular weight of 26,200. It was found that polymer (A-2) contained an average of 0.7 trimethoxysilyl groups at each end and an average of 2.1 trimethoxysilyl groups per molecule.

[0112] Synthesis Example 3 A synthesis example of polymer (A-3) is shown below.

[0113] Using polyoxypropylene glycol with a number-average molecular weight of approximately 4,500 as an initiator, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene with a number-average molecular weight of 25,500 and a molecular weight distribution Mw / Mn = 1.32. Subsequently, 1.2 molar equivalents of sodium methoxide were added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene as a 28% methanol solution. After distilling off the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene to convert the terminal hydroxyl groups to allyl groups, and unreacted allyl chloride was removed by vacuum devolatilization. The resulting unpurified polyoxypropylene was mixed and stirred with n-hexane and water, followed by centrifugation to remove the water. The metal salts in the polymer were removed by vacuum devolatilization of the hexane from the resulting hexane solution. This yielded a polyoxypropylene having allyl groups at its termini. To 500 g of this polymer, 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt % isopropanol solution calculated as platinum) was added, and 4.5 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-3) having terminal dimethoxymethylsilyl groups and a number-average molecular weight of approximately 26,500. Polymer (A-3) was found to have an average of 0.7 dimethoxymethylsilyl groups at each terminal and an average of 1.4 dimethoxymethylsilyl groups per molecule.

[0114] Synthesis Example 4 A synthesis example of polymer (A-4) is shown below.

[0115] Using an initiator containing polyoxypropylene glycol having a number average molecular weight of approximately 4500 and polyoxypropylene triol having a number average molecular weight of approximately 4500 in a 50 / 50 weight ratio, propylene oxide was polymerized in the presence of a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene having a number average molecular weight of 19,700 and a molecular weight distribution Mw / Mn = 1.33. Subsequently, 1.2 molar equivalents of sodium methoxide were added as a 28% methanol solution relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene. After distilling off the methanol by vacuum devolatilization, an additional 1.5 molar equivalents of allyl chloride was added relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene to convert the terminal hydroxyl groups to allyl groups, and unreacted allyl chloride was removed by vacuum devolatilization. The resulting crude polyoxypropylene was mixed with n-hexane and water and stirred, followed by centrifugation to remove the water. The hexane was then devolatilized under reduced pressure from the resulting hexane solution to remove metal salts from the polymer. This yielded polyoxypropylene having allyl groups at its termini. 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt % platinum equivalent isopropanol solution) was added to 500 g of this polymer, and 6.5 g of dimethoxymethylsilane was slowly added dropwise while stirring. The resulting mixture was reacted at 100°C for 2 hours, after which unreacted dimethoxymethylsilane was distilled off under reduced pressure to yield polyoxypropylene (A-3) having dimethoxymethylsilyl groups at its termini and a number-average molecular weight of approximately 19,900. Polymer (A-3) was found to have an average of 0.7 dimethoxymethylsilyl groups at each terminus and an average of 1.8 dimethoxymethylsilyl groups per molecule.

[0116] Synthesis Example 5 A synthesis example of polymer (A-5) is shown below.

[0117] Using polyoxypropylene glycol with a number average molecular weight of approximately 4,800 as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene having a number average molecular weight of 27,900 and a molecular weight distribution Mw / Mn = 1.21 and a hydroxyl-terminated terminal group. Subsequently, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene. After distilling off the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added relative to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the reaction was carried out at 130°C for 2 hours. Subsequently, 0.28 molar equivalent of a methanol solution of sodium methoxide was added to remove the methanol, and 1.79 molar equivalents of allyl chloride was added to convert the terminal hydroxyl groups to allyl groups. The resulting crude polyoxypropylene was mixed with n-hexane and water and stirred, followed by centrifugal separation to remove the water. The resulting hexane solution was then devolatilized under reduced pressure to remove the metal salts from the polymer. This yielded polyoxypropylene having multiple terminal carbon-carbon unsaturated bonds. The resulting polymer was found to have an average of 2.0 terminal carbon-carbon unsaturated bonds.

[0118] To 500 g of the resulting polyoxypropylene having multiple terminal carbon-carbon unsaturated bonds, 50 μl of a platinum divinyldisiloxane complex solution (a 3 wt % isopropanol solution calculated as platinum) was added, and 9.6 g of dimethoxymethylsilane was slowly added dropwise with stirring. The resulting mixture was reacted at 100°C for 2 hours, and then unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-5) having multiple terminal dimethoxymethylsilyl groups and a number-average molecular weight of 28,500. It was found that polymer (A-5) had an average of 1.7 dimethoxymethylsilyl groups per terminal, and an average of 3.4 dimethoxymethylsilyl groups per molecule.

[0119] Synthesis Example 6 A synthesis example of polymer (A-6) is shown below.

[0120] The inside of a stainless steel reactor equipped with a stirrer was deoxygenated, and 7.9 g of cuprous bromide, 125 g of n-butyl acrylate, 37 g of ethyl acrylate, and 38 g of stearyl acrylate were charged and heated with stirring. 90 g of acetonitrile and 16.4 g of diethyl 2,5-dibromoadipate as an initiator were added and mixed. The temperature of the mixture was adjusted to approximately 80°C, and then pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the polymerization reaction. 502 g of n-butyl acrylate, 146 g of ethyl acrylate, and 152 g of stearyl acrylate were sequentially added to proceed with the polymerization reaction. Additional triamine was added as needed during the polymerization to adjust the polymerization rate. The total amount of triamine used during the polymerization was 1.5 g. The polymerization was allowed to proceed while adjusting the internal temperature between approximately 80°C and approximately 90°C. When the monomer conversion (polymerization reaction rate) reached approximately 95% or higher, the volatile matter was removed by devolatilization under reduced pressure to obtain a polymer concentrate. To this concentrate, 200 g of 1,7-octadiene (hereinafter abbreviated as diene or octadiene), 360 g of acetonitrile, and 3.2 g of triamine were added. The mixture was heated and stirred for several hours while adjusting the internal temperature to about 80°C to about 90°C, to react the octadiene with the polymer terminals. The acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure, yielding a polymer concentrate having alkenyl groups at the terminals.

[0121] The concentrate was diluted with butyl acetate, and a filter aid, an adsorbent (Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd.), and a hydrotalcite (Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd.) were added. The mixture was heated to about 80 to 100°C with stirring, and the solid components were then filtered off. The filtrate was concentrated to obtain a crude polymer. The crude polymer, a heat stabilizer (Sumilizer GS, Sumitomo Chemical Co., Ltd.), and an adsorbent (Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd.) were then added, and the mixture was heated and stirred under reduced pressure, followed by devolatilization and heating. The mixture was heated and stirred at a high temperature of about 170°C to about 200°C for several hours, and then heated and stirred under reduced pressure. The adsorbent (Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd., Kyowa Chemical Co., Ltd.) was then added, and about 10 parts by weight of butyl acetate was added to the polymer. The mixture was then heated and stirred at a high temperature of about 170°C to about 200°C for several hours. The treated solution was further diluted with butyl acetate, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

[0122] 500 g of the polymer obtained by the above method was mixed with 13 g of dimethoxymethylsilane (DMS), 4 g of methyl orthoformate (MOF), and 5 mg of a platinum catalyst [an isopropanol solution of bis(1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst; hereinafter, referred to as "platinum catalyst"], and the mixture was heated and stirred to approximately 100°C. After heating and stirring for approximately 1 hour, unreacted DMS and other volatile components were removed by vacuum distillation to obtain a (meth)acrylic acid ester copolymer (A-6) having dimethoxymethylsilyl groups at both ends. The resulting polymer (A-6) had a number average molecular weight of 26,100, a molecular weight distribution of 1.3, and 1.7 silyl groups introduced per molecule.

[0123] [Examples 1 to 12, Comparative Examples 1 to 3] Component (A), component (B), and component (C) or needle filler shown in Table 1 were added to a mixing container and mixed using a mechanical stirrer at 600 rpm for 10 minutes at 25°C. The resulting mixture was evaluated for emulsification. The results are shown in Table 1.

[0124] [Results] Table 1 shows that the emulsion compositions of Examples 1 to 12 could be uniformly emulsified, while the emulsion compositions of Comparative Examples 1 to 3 could not be emulsified and separated (no emulsion was obtained).

[0125] Therefore, it has been demonstrated that one embodiment of the present invention can provide an emulsion composition that can easily form an emulsion containing a hydrolyzable silyl group-containing polymer.

[0126] The present emulsion composition can provide an emulsion composition that can easily form an emulsion containing a hydrolyzable silyl group-containing polymer, and therefore can be suitably used in fields such as cement mortar.

Claims

1. (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water; (C) a layered filler; Including, the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) has a structure derived from polyoxypropylene diol or polyoxypropylene triol, the weight ratio of the component (A) to the component (B) is 40:60 to 60:40; An emulsion composition comprising 1.5 to 20 parts by weight of the component (C) per 100 parts by weight of the total of the components (A) and (B).

2. The emulsion composition according to claim 1 , wherein the component (C) is a synthetic product.

3. (A) at least one of a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2), (B) water; (C) a layered filler, and a stirring step of mixing and stirring 1.5 to 20 parts by weight of the component (C) with 100 parts by weight of the total of the component (A) and the component (B), the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) has a structure derived from polyoxypropylene diol or polyoxypropylene triol, A method for producing an emulsion composition, wherein the weight ratio of the component (A) to the component (B) is 40:60 to 60:

40.

4. 4. The method for producing an emulsion composition according to claim 3, wherein in the stirring step, the rotation speed of the stirring device is 200 to 1800 rpm and the stirring time is 1 to 60 minutes.

5. The method for producing an emulsion composition according to claim 3, wherein the stirring temperature in the stirring step is 5 to 80°C.

6. The method for producing an emulsion composition according to claim 3 , wherein the component (C) is a synthetic product.