TW201041645A - Water-based emulsion - Google Patents

Abstract

Provided is a water-based emulsion containing the following component (A), component (B) and component (C). (A) an acrylic resin containing a structural unit originating from α, β-unsaturated carboxylic acid, and a structural unit originating from α, β-unsaturated carboxylic acid ester derived from a C-1-10 aliphatic alcohol having an amine group which may have a substituent and an α, β-unsaturated carboxylic acid, wherein a hydrophile ratio of the acrylic resin is 9 to 12 (wherein the hydrophile ratio of the acrylic resin is a weight average of hydrophile ratios of monomers deriving the structural units of the acrylic resin, provided that the hydrophile ratio of a monomer is a value calculated from the following formula: hydrophile ratio of a monomer=20x(formula weight of hydrophilic portion of the monomer)/(molecular weight of the monomer)) (B) thermoplastic polymer (C) water.

Description

201041645, VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to an aqueous emulsion. 1 [Prior Art] Polypropylene is used for automotive components such as bumpers because of its excellent workability and strength. In automotive parts, coatings are usually applied for decoration or the like. However, since the surface of the polypropylene is difficult to adhere to other materials such as paints, a chlorinated polyolefin excellent in adhesion to polypropylene is generally coated on the polypropylene, and a coating is applied thereon (for example: Refer to 曰本特开平5-7832号). SUMMARY OF THE INVENTION The present invention provides the following: ' <1> An aqueous emulsion comprising the following components (A), (B) and (C): Component (A): comprising alpha, stone- a structural unit of an unsaturated carboxylic acid, and an aliphatic alcohol oxime having a carbon number of 1 to 10 which may have a substituent-containing amine group, and α,/5 derived from /3 -unsaturated acid. An acrylic resin having a structural unit of an unsaturated carboxylic acid ester, wherein the acrylic resin has a hydrophilic ratio of 9 to 12 (here, the hydrophilic ratio of the acrylic resin is derived from the acrylic acid system) The weight average of the hydrophilic ratio of the monomer of the structural unit of the resin, and the hydrophilic ratio of the monomer is a value calculated by the following formula: Hydrophilic ratio of the monomer = 20 χ (the amount of the hydrophilic portion of the monomer) / ( Molecular weight of monomer)); Component (Β): Thermoplastic polymer; 4 321925 201041645 &quot; Ingredient (c): Water. The aqueous emulsion according to <1>, wherein the component (B) comprises a thermoplastic polymer having a structural unit derived from ethylene and/or propylene. <3> The aqueous emulsion according to <1>, wherein the component (B) comprises: a structural unit derived from ethylene and/or propylene and derived from the formula (I) CH2=CH-R (I) In the copolymer of the structural unit of the vinyl compound represented by the formula (wherein R represents a 2nd alkyl group, a 3rd alkyl group or an alicyclic hydrocarbon group), α, a cold-unsaturated carboxylic anhydride hydrazine is graft-polymerized. The resulting polymer. The aqueous emulsion of the formula (I), wherein the vinyl compound is a vinyl cyclohexane, as described in <3>. The aqueous emulsion according to any one of <1> to <4>, wherein the component (B) is a MFR (melt flow rate) (190 ° C, 2.16). Kgf) A thermoplastic polymer of 130 g/10 min or more and 300 g/10 min or less. The aqueous emulsion according to any one of the above-mentioned (A) and the component (B) is a dispersoid and the component (C) is the above-mentioned component (C). In the case of the dispersion medium, the volume-based median diameter of the dispersoid (median diameter AO.Olvu^S/zm. &lt;7&gt;, the aqueous emulsion according to any one of &lt;1&gt; to &lt;6&gt; Wherein the structural unit derived from an aliphatic alcohol having from 1 to 10 carbon atoms having a substituent-containing amino group and α, a cold-unsaturated carboxylic acid derived from a methyl group An aqueous emulsion according to any one of <1> to <7>, which is derived from α, 5 321925 201041645 'unsaturated. The structural unit of the carboxylic acid is a structural unit derived from acrylic acid or mercaptoacrylic acid. <9> A method for producing an aqueous emulsion characterized in that the obtained molten mixture is obtained by melt-kneading the component (A) and the component (B). Mixed with water; component (A): a structural unit derived from α, a non-unsaturated carboxylic acid, and a source An acrylic resin derived from an aliphatic alcohol having a number of carbon atoms which may have a substituent, and an aliphatic alcohol, which is derived from α,/3-unsaturated tarenic acid, and α-, alkaloid-unsaturated Wherein the hydrophilicity of the acrylic resin is 9 to m. Here, the hydrophilic ratio of the acrylic resin is the weight average of the hydrophilic ratio of the monomer derived from the structural unit of the acid resin. The value calculated by the following formula: The hydrophilic ratio of the early monomer = 20x (single 俨 10, Μ \ , , sub-quantity)). The amount of the hydrophilic part of the flat body / (the sub-component of the monomer) (Β): thermoplastic polymer; component (C): water. 〇 &lt;10&gt;-type hardened material' is obtained by drying a cerium to lanthanum emulsion. The laminated body 'system has: at least one selected from wood a material, a fiber material, a plastic material, a ceramic material, and a metal material. The substrate layer composed of the material and the cured material described in (10) <12> A method for manufacturing a laminate, The system comprises the following steps: Tao Xing ^ to ^ species selected from wood materials, cellulosic materials, plastic materials, _ / And the aqueous layer emulsion according to any one of &lt;1&gt; to &lt;8&gt;, which is obtained by the material in the group of the metal materials, and the substrate layer and the substrate layer a step of laminating the aqueous emulsion layer; and drying the laminate obtained in the above step to obtain a laminate having the substrate layer and the cured layer obtained from the aqueous emulsion. - &lt; 13 &gt; An agent comprising a structural unit derived from a &lt;2, /5-unsaturated acid, and an aliphatic alcohol having a carbon number of 1 to 10 derived from a group having a substituent, and a, an unsaturated carboxylic acid The acrylic resin of the structural unit of the α, /5-unsaturated carboxylic acid ester derived from the acid is used as an active ingredient, and the hydrophilic ratio of the acrylic resin is 9 to 12 (here, the hydrophilicity of the acrylic resin) The ratio is the weight average of the hydrophilic ratio of the monomer derived from the structural unit of the acrylic resin, and the hydrophilic ratio of the monomer is a value calculated by the following formula: Hydrophilic ratio of the monomer = 20 Å (the hydrophilicity of the monomer) Part of the amount) / (single part Sub-quantity)). <14> The emulsifier according to <13>, which is derived from an aliphatic alcohol having 1 to 10 carbon atoms which may have an amine group which may have a substituent Q, and an α, stone-unsaturated carboxylic acid The structural unit of the α,stone-unsaturated carboxylic acid ester is a structural unit derived from ruthenium methacrylate, ruthenium-diguanylaminoethyl ester. The emulsifier according to <13> or <14>, wherein the structural unit derived from the α, /3-unsaturated carboxylic acid is derived from a group selected from the group consisting of acrylic acid and methacrylic acid. At least one of the structural units. The use of the aqueous emulsion according to any one of <1> to <8>, which is selected from at least one selected from the group consisting of wood materials, cellulosic materials, plastic materials, ceramic materials, and A hardened layer is formed on the base material layer 7 321925 201041645 which is composed of a material in a group of metal materials. [Embodiment] The aqueous emulsion of the present invention comprises the following components (Α), component (8), and component (6). Ingredient (Α). Contains a structural unit derived from an α'厶-unsaturated carboxylic acid (hereinafter referred to as a structural unit (al)), and q is derived from a fat having a substituent having an amine group of 1 to 1 G. (d) derived from α, unsaturated (four)

Ο α' stone-unsaturated citric acid vinegar structural unit (hereinafter referred to as structural unit (a2)) of the acrylic resin's towel, the (four) acid system of the purpose of the hydrophilic ratio = 9,12 (here 'c (4) The hydrophilic ratio of the resin is the hydrophilicity of the monomer derived from the structural unit of the propylene = resin, and the hydrophilic ratio is the value calculated by the following formula: the monthly mean hydrophilic ratio of the monomer = 2 〇χ (single The amount of the body. The amount of the hydrophilic part) / (the component of the monomer (Β): thermoplastic polymer; the component (C): water. First, the component (Α) is explained. ^ The component contains the structural unit ( Al) and propylene fluorene resin of structural unit (a2). Derivative structure list (alka, stone-unsaturated oxic acid can be cited as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, f-acid , itaconic acid, jingkang, angelic acid, sorbic acid, and other carbon atoms with a carbon number of 3矣20, a stone-unsaturated nucleus. The α, ^ unsaturated carboxylic acid has 1 Or 2 fluorenyl (-C00H) unsaturated decanoic acid is preferred. 321925 8 201041645 The acrylic resin of the component (A) can have 2 kinds of The structural unit (al). The structural unit (al) is preferably at least one selected from the group consisting of structural units derived from acrylic acid and • structural units derived from methacrylic acid. 'Derivative structural unit (a2) The α,/5-unsaturated carboxylic acid ester is derived from an aliphatic alcohol having 1 to 10 carbon atoms which may have a substituent, and an α,/3-unsaturated carboxylic acid. The same as the above Q, and preferably acrylic acid or methacrylic acid. The amine group which may have a substituent may, for example, be an amine group, a methylamino group, an ethylamino group, an propylamino group or an isopropylamine group. Amino group having one linear, branched chain or cyclic alkyl group having 1 to 10 carbon atoms, such as butylamine, isobutylamino, butylamino, and butylamino Diaminoamine, mercaptoethylamino, diethylamino-propyl-propyl group has two linear, branched or cyclic alkyl groups of 1 to 1 Å. And a cyclic amine group in which a decyl group having a linear, branched chain or cyclic alkyl group having 2 slave atoms 丨 to 1 为 is preferred to have 2 carbons The amine group having a linear, branched or cyclic alkyl group having an atomic number of i to 3 is more preferable. The aliphatic alcohol having 1 to 10 carbon atoms may, for example, be decyl alcohol or ethanol.

Propanol, isopropanol, butanol, tert-butanol, pentanol, 3-mercaptobutanol, H-dimethylpropanol, 3-methyl-2-butanol, 2-ethylhexanol, hydrazine a linear, branched chain or cyclic aliphatic alcohol having 1 to 1 carbon atom such as an alcohol, a decyl alcohol or a cyclohexanol, which has a linear number of carbon atoms of 4 or a branched chain or Ring ^ aliphatic alcohol is preferred. &lt; An aliphatic alcohol having a carbon atom group having a substituent which may have a substituent of from 1 to 1 321 321 925 9 201041645, and examples thereof include N,N-dimethylaminoethanol and N,N-diethylaminoethanol , N-methyl-N-ethylaminoethanol, N,N-dipropylaminoethanol, N-mercapto-N-propylaminoethanol, N-ethyl-N-propylaminoethanol, N, N-dimethyl Aminopropanol and N,N-•dimethylaminobutanol. An anthracene derived from an aliphatic alcohol having 1 to 10 carbon atoms having a substituent group and an α-unsaturated carboxylic acid; the point-unsaturated carboxylic acid ester may, for example, be cerium acrylate. Ν-diethylaminoethyl ester, hydrazine methacrylate, hydrazine-diethylaminoethyl acrylate, hydrazine acrylate, hydrazine-diguanidinoethyl ester, decyl propyl decanoate Ν, Ν-dimethyl hydrazine Ester, fluorenyl-fluorenyl-hydrazine-ethylaminoethyl acrylate and hydrazine-methyl-hydrazine-ethylaminoethyl methacrylate, and ν, Ν-dimethylaminoethyl methacrylate It is better. The acrylic resin of the component (Α) may have two or more structural units (a2). The content of the structural unit (al) in the acrylic resin of the component (A) is generally 20 to 99 moles, and 50 to 99 moles per mole of the structural unit 1 constituting the acrylic resin. It is better. The content of the structural unit (&amp; 2) in the acrylic resin of the component (A) is generally 1 to 80 m, and 1 to 50 m with respect to the entire structural unit constituting the acrylic resin. The ear is better. The acrylic resin of the component (A) may contain two or more kinds of propionic acid resins. The acrylic resin of the component (Α) may have other structural units in addition to the structural unit (al) and the structural unit (a2). Other structural units include, for example, a source free carbon atom 丨 to 2 〇 10 321 925 201041645 an aliphatic alcohol and an α I unsaturated (d) derived α ester structural unit (hereinafter referred to as 楢, unsaturated carboxy 醆 1 Manxin Bu 昨 昨 (10)), the source of free carbon atoms 0 eve of the Japanese aliphatic alcohol and α,/5-unsaturated _ derived stone-unsaturated carboxylic acid ester structure, rK9,, r η 1 ^早兀 (hereinafter referred to as tectonic unit: 2)): The source free has the number of carbon atoms in the (four) group. And H-unsaturated "_ raw aj_ unsaturated unit (hereinafter referred to as structural unit (10)), and source free poly St Ο ❹ unsaturated (four) derived ", ^ unsaturated (four) (four) structural unit (hereinafter referred to as structural unit) (b4)) The H-unsaturated (four) derived from the above other structural units may be the same as those described above, and preferably the propionic acid or methyl procyanoic acid. The structure of the k-unit 70 (10) α, point _ The saturated acid vinegar is derived from an aliphatic alcohol having 1 to 20 carbon atoms and an α, 10,000-unsaturated carboxylic acid. The aliphatic alcohol having 1 to 20 carbon atoms may, for example, be methanol, ethanol or propanol. Isopropanol, butanol, tert-butanol, pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 3-methyl-2-butanol, 2-ethylhexanol, hydrazine a linear, branched chain or cyclic fat having 1 to 20 carbon atoms such as an alcohol, a sterol, a dodecanol, a tridecyl alcohol, a hexadecanol, an octadecyl alcohol or a cyclohexanol. Alcohols. Alpha, stone-unsaturated carboxylic acid esters derived from an aliphatic alcohol having a stone inverse number of 1 to 20 and α, unsaturated citric acid may, for example, be methyl acrylate, ethyl acrylate or propylene. Propyl ester, butyl acrylate, amyl acrylate, 3-methylbutyl acrylate, 2,2-dimethylpropyl acrylate, 3-methyl-2-butanyl acrylate, 2-ethylhexyl acrylate, acrylic acid Oxime ester, decyl acrylate, dodecyl acrylate, tridecyl acrylate, hexadecyl acrylate, acrylic acid 18 321925 11 201041645 , ester, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate Propyl methacrylate, butyl methacrylate, amyl methacrylate, 2-methyl-2-butyl methacrylate, 2-ethylhexyl methacrylate, τ-based • Acetate vinegar, methyl Acrylate acrylate, decyl acrylate decanoic acid, methyl acrylate tridecyl vinegar, hexadecyl methacrylate, methacrylic acid octadecyl acrylate and cyclohexyl acrylate. The acrylic resin of component (A) may contain Two or more structural units (M). ^ The α,/5-unsaturated carboxylic acid ester of the derived structural unit (b2) is composed of a polyhydric aliphatic alcohol having 1 to 10 carbon atoms and α,/3 -unsaturated Derived by an acid, the polyhydric alcohol having 1 to 10 carbon atoms may, for example, be hydroxymethanol , hydroxyethanol, hydroxypropanol, hydroxybutanol, hydroxypentanol and hydroxyhexanol. Derived from a polyhydric aliphatic alcohol having 1 to 10 carbon atoms and an α,/3-unsaturated carboxylic acid: 10,000- Examples of the unsaturated carboxylic acid ester include hydroxy acrylate, acrylic acid, propyl benzoic acid, acrylic acid, butyl hydroxy valerate, hydroxy hydroxy acrylate. Ester, hydroxydecyl methacrylate, hydroxyethyl methacrylate, propyl methacrylate, hydroxybutyl methacrylate, hydroxy amyl methacrylate and hydroxyhexyl methacrylate. The acrylic resin may contain two or more structural units (10). The structural unit (b3) is derived from an aliphatic alcohol having a carboxylic acid group of 1 to 10 and an α,/5-unsaturated acid. α,/5 - unsaturated tartrate. The "carboxylic acid group" herein means an organic group having a carboxyl group (-COOH), and examples thereof include a carboxymethyl group, a 1,2-dicarboxyethyl group, a 2-carboxyphenyl group, and a 2,3-two 12 321925 201041645, carboxyphenyl. The number of carbon atoms with this decanoic acid group! The α,β-unsaturated carboxylic acid ester derived from the aliphatic alcohol to 10 and the /5-unsaturated carboxylic acid may, for example, be a succinic acid 2-propenyloxy ethoxy group, (4) 2 _(tetra) fluorenyloxy B. From the purpose, the station acid • 2_methyl propyl oxy-S, and 2-methyl propyl oxy-acetate. The acrylic resin of the component (A) may contain two or more kinds of structural units (10).构造 The structural unit (b4) is derived from a free polyalkylene glycol and a (2,/5-unsaturated carboxylic acid ester derived from a cold-unsaturated carboxylic acid. The polyglycol diol is a polyethylene glycol or a polypropylene glycol. , polyethylene glycol polypropylene glycol, polyethylene glycol polytetramethylene glycol, • methoxy polyethylene glycol, etc., through an oxygen atom, bonding 1 to 50 alkyl groups having 1 to 4 carbon atoms The polyalkylene glycol and the hydroxyl group at the terminal of the polyalkylene glycol can be protected by an alkyl group having 1 to 2 carbon atoms, an acryloyl group, a methacrylic group, or the like. Y5_α derived from unsaturated carboxylic acid, not “unsaturated” and carboxylic acid esters, for example, polypropylene glycol acrylate, polyethylene glycol acrylate, polyethylene glycol polypropylene glycol ester, polyacrylic acid polyethyl acrylate Glycol polytetramethylene glycol ester, decyl acrylate polyethylene glycol ester, polypropylene glycol methacrylate, polyethylene glycol methacrylate, methacrylic acid polyethylene glycol polypropanol S 曰, single Mercaptoacrylic acid polyethylene glycol polytetramethylene glycol vinegar and methoxy polyethylene glycol methacrylate. The acrylic resin of the component (Α) It is preferable to have a structural unit (bl) or a structural unit (b3), and it is preferable to contain a structural unit (bl) and a structural unit (b3). 321925 13 201041645 When the acrylic resin of the component (A) contains a structural unit (bl When the content of the structural unit (bl) is generally 5 to 95 moles, preferably 10 to 80 moles, relative to the entire structural unit 100 constituting the acrylic resin. The acrylic of the component (A). The content of the structural unit (b2) in the resin is generally 0 to 50 m, relative to the entire structural unit constituting the acrylic resin, preferably 0 to 30 m, and 0 to 1 mol. The content of the structural unit (b3) is generally 0. 1 with respect to the total structural unit 100 constituting the acrylic resin, the content of the structural unit (b3). To 80 mol, preferably 5 to 40 mol. The content of the structural unit (b4) in the acrylic resin of the component (A) is generally 0 with respect to the entire structural unit 100 constituting the acrylic resin. Up to 50 m, preferably 0 to 30 m, and 0 to 1 In the acrylic resin of the component (A), the content of the structural unit having an anionic group such as the structural unit (al) or the structural unit (b3), the cured product obtained from the aqueous emulsion of the present invention, and the polypropylene From the viewpoint of the structure, it is preferably 45 to 85 mol, more preferably 50 to 80 mol, based on the entire structural unit 100 constituting the acrylic resin. The acrylic resin as the component (A), With respect to all of the structural units 100 constituting the acrylic resin, a structural unit (al) containing 5 to 80 moles, a structural unit (a2) of 1 to 50 moles, and 10 to 80 moles of 14 321925 201041645 The structural unit (bl) and the structural unit (b3) of 5 to 30 moles and the structural units (al), (a2), (bl), and (b3) are preferably 100-mole acrylic resin. The acrylic resin of the component (A) may contain a structural unit derived from ethylene, a structural unit derived from propylene, a structural unit derived from a linear olefin having 4 or more carbon atoms described below, and derived from the following formula ( The structural unit of the vinyl compound shown in I), the structure derived from the following addition polymerizable monomer, and the like, but the content is such that it is nondestructive and the adhesion of the cured product obtained from the aqueous emulsion of the present invention. The amount of the structural unit may be about 5 m or less with respect to all the structural units constituting the acrylic resin, and the structural unit derived from the monomer which can be added and polymerized is preferably 1 mol or less. . The acrylic resin of the component (Α) can be produced by subjecting a monomer derived from each structural unit to addition polymerization. For example, a solvent such as an alcohol solvent such as isopropyl alcohol or water may be mixed with a monomer, and the polymerization initiator such as the obtained mixture and a radical initiator may be usually 70 to 100 ° C and 75 to 95 °. a method in which C is preferably mixed at a temperature of 75 Torr to 85 ° C, and the resulting mixture is subjected to polymerization by stirring for about 1 to 24 hours; the solvent and a part of the monomer are mixed, and the obtained The mixture is mixed with the residual monomer and the residual monomer at 70 to 100 ° C, preferably 75 to 95 ° C, more preferably 75 to 85 ° C, and the resulting mixture is passed through generally 1 to 24 hours. A method of carrying out a polymerization reaction by stirring left and right. In order to easily control the polymerization reaction, a solution obtained by dissolving a polymerization initiator or a residual monomer in an organic solvent may also be used. The amount of the polymerization initiator to be used is 100 parts by weight relative to the total amount of the monomers. 15 321925 201041645 parts ' is generally 0.01 to 5 parts by weight, preferably 2 to 3 parts by weight. The polymerization initiator may, for example, be: 2, 2,-azobisisobutyronitrile, 2 2 , methacrylonitrile, ", - (a cyclohexane): 2, 2, _虱 one (2,4-monomethylvaleronitrile), 2,2'-azobis(24_diindole_4_:::), dimethyl-2,2, _diox Azo compounds such as 2~methylpropionic acid vinegar, [2'_-methylpropionitrile); peroxidized laurel, hydroquinone, benzotriphenyl, benzoyl peroxide, benzoic acid benzoic acid Ester, cumene hydroperoxide, peroxidic acid disulfide, dipropylene glycol peroxydicarbonate, tributyl vinegar peroxy neodecanoic acid, third vinegar peroxypivalate, ?(3 , 5'5-trimethyl hexanyl) an organic peroxide such as a peroxide; and an inorganic peroxide such as a persulfate clock, ammonium persulfate or hydrogen peroxide. A redox initiator (redGx^仏) which is used together with a polymerization initiator and a reducing agent can also be used as a polymerization initiator. The acrylic resin has a hydrophilic ratio of from 9 to 12, preferably from 9.1 to π, more preferably from 9 Å to 1 Torr. The aqueous emulsion J of the present invention containing the acrylic resin having a polymer affinity in the above-mentioned range is, for example, dried at a temperature of from about 90 C to about 120, thereby imparting a cured product excellent in adhesion to a substrate such as propylene. Further, even if the drying temperature is at a low temperature of about 9 Torr, it is possible to impart a cured product excellent in adhesion to a substrate such as propylene. The polymer hydrophilic ratio of the acrylic resin is the weight average of the hydrophilic ratio of the monomer derived from the structural unit of the acrylic resin, and the hydrophilic ratio of the monomer is calculated by the following formula. The hydrophilic ratio of the monomer = 2 〇χ (the amount of the hydrophilic portion of the monomer) / (the monomer is divided into 321925 16 201041645 sub-quantity)) The hydrophilic portion of the monomer refers to the carboxyl group (_C00H), hydroxyl group in the monomer ( -0H), a polar moiety such as an amine group (-), a sulfonic acid group (-s〇3H), a carbonyloxy group (-c〇2-), or a nitrogen atom (N) of a dialkylamino group (-NR2). The amount of the carboxyl group is 45. 02, and the amount of the hydroxyl group is 17. 〇2, the formula of the amine group is 16.02, the formula of the sulfonic acid group is 81.07, the formula of the carbonyloxy group is 44.01, and the amine of the second compound is The formula of the nitrogen atom is hoi. 5。 The hydrophilic ratio of the acrylic acid is 12. 5, because the acrylic acid (molecular weight: 72. 06) has a carboxyl group as a hydrophilic part. Hydrophilic ratio of acrylic acid = 20x45. 02/72. 06=12. 5 For example: 2-methylpropenyloxyethyl succinate (molecular weight: 230.21) with 1 thiol and 2 methoxy groups as hydrophilic In part, the hydrophilic ratio of 2-methacryloxyethyl succinate is 1丨.6. Hydrophilic ratio of 2-methylpropenyloxyethyl succinate = 2〇χ133. 〇4 /230.21=11.6 For example: due to N,N-dimethylaminoethyl methacrylate (molecular weight: 157·21) The nitrogen atom of one carbonyloxy group and the dialkylamine group is a hydrophilic portion, so the hydrophilic ratio of N,N-dimethylaminoethyl methacrylate is 7 4 . The hydrophilic ratio of N,N-dimethylaminoethyl methacrylate = 20x58. 02/ 157. 21=7. 4 In the same way, the hydrophilic ratio of decyl methacrylate is 8 8 'decyl methacrylate 5。 The hydrophilic ratio was 3.5, the hydrophilic ratio of tridecyl methacrylate was 3.3. 0重量份。 By way of example, by weight of 24. 5 parts by weight of acrylic acid 2-mercaptopropyl 321925 17 201041645 olefinic ethyl oxyethyl 22.5 parts by weight, N,N-diguanidinoethyl methacrylate 20.8 parts by weight Ethyl methacrylate 15. 〇 by weight, 3.8 parts by weight of lauryl methacrylate and 13 g of methyl-acid; 6.2 parts by weight of the polymer obtained by polymerization of the acrylic resin has a hydrophilic ratio of 9.4. Hey. The hydrophilic ratio of the polymer of the acrylic resin = (12 5χ24. 5+11·6χ 22. 5 + 7. 4 χ 28. 0 + 8. 8 χ 15. 〇+ 3. 5 χ 3. 8 + 3. 3 χ 6. 2) / 100=9. 40 The content of the structural unit derived from the monomer of the high hydrophilic ratio derived from the acrylic acid or the amber sputum into the U Τ丞 (eight) seed milk roll G and the low hydrophilicity The content of the structural unit of the carcass of the ratio is appropriately adjusted, and the acrylic acid-based resin having a hydrophilic ratio of the polymer of the acrylic tree of 9 to 12 can be prepared. In the aqueous emulsion of the invention, it is used as an emulsifier for the knife (C). Invention == Contains ingredients (Α), and it is more preferable to contain water. This ammonia is preferred. The emulsification of the present invention refers to the "muscle neutralization degree" of the relative enthalpy to 2Gi)m == the ratio of the single cation having the anionic group contained in the number of the "2" The number of ears is second, and the component (Β) is explained. The composition (Β) is a thermoplastic polymer, a thermoplastic polymer of a potted structural unit, and a thermal hybrid polymer, such as an active 7L, which is derived from vinegar wax and palm wax. , Fischer-Tropsch 321925 18 201041645 (Fischer-Tropsch) waxes, microcrystalline waxes, paraffin waxes, and thermoplastic polymers of structural units such as oxides, low molecular weight polyamines, and fatty guanamines. The thermoplastic polymer is preferably a thermoplastic polymer containing a structural unit derived from ethylene and/or propylene. The thermoplastic polymer containing structural units derived from ethylene and/or propylene may be, for example, low-density polyethylene. Polyethylene, polyethylene, bismuth-acetic acid, ethylene-copolymer, ethoxylate, ethyl acetate, acetic acid, ethylene glycol, eupolymer, ethylene-acrylic acid copolymer, ethylene-propylene-acrylic acid Copolymer, ethylene-acrylic acid vinegar copolymer, ethylene-propylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethyl acetonitrile-acrylic acid copolymer, baking Methyl-ester copolymer, ethylene-propylene-methacrylate copolymer, polypropylene, ethylene-propylene copolymer, ethylene-hexadiene copolymer, propylene-hexane copolymer, ethylene-propylene a hexene copolymer, an ethylene-butene copolymer, a propylene-butylene copolymer, an ethylene-propylene-butadiene copolymer, and the maleic acid wild modification. a copolymer containing a structural unit derived from a woman and/or propylene and a structural unit derived from a compound of the formula (1) (hereinafter referred to as an ethylenic compound (1)) (hereinafter referred to as a polymer) (B-1)), and a polymer obtained by graft-polymerizing α-n- and a slow-acid needle with a polymer (β-υ) (hereinafter referred to as a polymer (β_2 is preferably. CH2=CH- R (!) (wherein, R represents a 2-stage alkyl group, a 3-stage appearance group or an alicyclic hydrocarbon group). R represents a second-order leuco group which is preferably a choline group having a carbon number of 3 to 2 Å, 3 The calcining base is preferably a 3-stage alkyl group having 4 to 2 carbon atoms, and the alicyclic ring 321925 19 201041645 is preferably a 3- to 16-membered ring-shaped hydrocarbon group. The (iv) type of smog group can be exemplified by: a cyclononyl group, a cyclodecyl group, and a cycloalkynyl group, preferably a cycloalkyl group. R is an alicyclic group of 3 to 2 G (3) having 3 to 2 carbon atoms, and a carbon number of 4 to 20 The alkyl group is more preferable. Examples of the vinyl compound include 3-methyl-butene, 3-mercapto-p-pentene, 3-methyl-1-hexene, and 3-methyl-1-heptene. , 3-indolyl q-octene, 3,4-dimethyl-p-pentene, 3, 4-di Methyl-p-hexene, 3,4-dimethyl-p-heptene, 3,4-monodecyl-octene, 3,5-dimercapto-1-hexene, 3,5-dimethyl 1-heptene, 3,5-dimethyl-1 -octyl, 3,6-dimethyl yheptene, 3,6-dimercapto-1-octene, 3,7-dimethyl 1-octene, 3, 4, 4-trimethyl-p-pentene, 3, 4, 4-trimethyl-1-hexene, 3, 4, 4-trimethyl-p-heptene, 3 a vinyl compound (I) wherein R is a 2nd alkyl group such as 4'4-trimercapto-1-octene; 3,3-dimercapto-1 -butene, 3,3-dimethyl-1 -pentene, 3,3-dimethyl-1-hexene, 3,3-dimethyl-1-heptene, 3,3-dimethyl-1-octene, 3, 3, 4_three Mercapto-1 -pentene, 3,3,4-trimethyl-1-hexene, 3,3,4-trimethylsulfonylheptene, 3,3,4-trimethyl-1-octene A vinyl compound (I) wherein R is a tertiary alkyl group; vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, etc. The vinyl compound (1) wherein r is a cycloalkyl group; vinyl adamantane, 5-vinyl-2-norbornene, and 4-ethylene-1-cyclohexene. Among them, preferred is 3- Mercapto-1-butene, 3-mercapto-1-pentene, 3-mercapto-1-hexene, 3,4-dimercapto-1-pentene, 3,5-dimercapto-p-hexene, 3'4'4 -trimethyl-1 -pentene, 3,3-didecylbutene, 3,3-dimethylene 20 321925 201041645-1-pentene, 3,3,4-tridecyl-1-pentene , vinyl cyclopentane, vinyl cyclohexane, vinyl cycloheptane, vinyl cyclooctane and 5-vinyl-2__ norbornazole; more preferably 3-mercapto-1-butene, 3 Monomethyl-1-pentene, 3,4-dimethyl-1-pentene, 3,3-dimethyl-1-butene, 3,3,4-tridecyl-1-pentene, Vinylcyclohexane and vinyl norbornene; particularly preferred are 3,3-dimethyl-1-butene and vinylcyclohexane, and more preferably vinylcyclohexane. The content of the structural unit derived from the vinyl compound (I) in the ruthenium polymer (B-1) is generally 5 to 40 with respect to all the structural units constituting the polymer (B-1). Mohr is preferably from 10 to 30 mols, more preferably from 10 to 20 mols, from the viewpoint of the adhesion of the cured product obtained by drying the aqueous emulsion of the present invention. The inner portion of the structural unit derived from the ethylenic compound (1) in the ruthenium polymer (B-1) can be determined by subjecting the polymer (B-1) to 1H-臓 analysis or I3c-NMR analysis.

Alkene, 1-pentadecene, 1-ene and 1-tap #1-octene are preferred.

20 321925 21 201041645: All construction units of the object (B?) 100 Mohrs - generally 95 to 60 Moto to 70 Molar% is better, 9 to 8 Mo is better. The unit poly σ may additionally have a structure derived from a monomer which can be added to the addition polymerization, a single system of ethylene, propylene, a large alpha olefin having 4 to 2 carbon atoms, and a vinyl compound (丨). a monomer other than a olefin, a propylene, a linear one with a carbon number of 4 to 20, and a second

The stagnation product (1) is added to the monomer of the merging, and the monomer has a carbon number of about 3 to 20. Specific examples of the monomer capable of addition polymerization include, for example, a ring # hydrocarbon, a compound of the formula (1), an olefin compound, a halogenated ethylene, an aliphatic carboxylic acid vinyl ester, an alkylene compound, and a cyanoethylene system. a compound, the above unsaturated carboxylic acid, the above α, a stone-unsaturated carboxylic acid g|, and a &amp;

(II) (wherein R and R&quot; each independently represent a linear, branched or cyclic alkyl group or a halogen atom having a carbon number of J to 18). Examples of the cycloolefins include cyclobutene, ring, ring (10), cyclosin, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-mercapto-2-norborner, 5_ethyl_2_norbornene, 5_butyl_2_norbornene, 5-phenyl-2-norborn, 5_benzenef-based_2 _Ice film woman, 2-tetracyclododecene, 2-tricyclic quinone, 2_tricyclotetraene, 2_five ring fifteen 321925 22 201041645

Alkene, 2-pentacyclohexadecene, methyl I production + one, method, 7 methyl I-tetracyclododecene, 8-ethyl-2-tetrazene distillate '2, norbornene, 5 -Ethyloxy-2,norbornene,5-methoxybenzyl-2-norborn κ secret ccm, c匕norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl- 5-methoxycarbonyl-2-lower# κ ”m~ piece~,5-cyano-2_norbornene, 8-&amp;, 碲8-methyl-8-methoxycarbonyl-2-tetracyclic Decadiene and 8-cyano-2-tetracyclo---, knee-gum ~ slightly ~, return. Among them, 'ring ring roast, cyclohexene, soil diarrhea, 2_ ice (four), 5 ~ methyl I Norborn 晞, phenyl phenyl-2, Ο Ο ❹ borneene, 2-tetracyclododecene, 2 1-2 j Rosin Λ ^ — decene, 2-tricycloundecene, 2 _ five ring埽, 2-pentahexaene, 5 fluorenyl _2—icing material, 5_ ke ke ke ke -2- borneol thin, 5 methoxy county _2 _ norbornene, 5-methyl-5 - Oxyfluoride-2-norbornium and 5-cyano-2_norborn are preferred, 2-norbornene and 2-tetracyclododecene are preferred. The olefin represented by formula (II) For example, isobutylene, 2-methyl-nonylbutene, 2-methyl+pentene, 2-methyl+hexene Alkene, &quot;base + heptareth, 2_methyl-1-octyl, 2'3-dimethyl+butene, 2,3-dimethylpentene, 2,3-dimethyl-1 -hexene, 2,3-dimethylene + heptene, 2,3-dimethyl + octyl, 2'4-dimethylpentene, 2,4,4-trimethyl-p-pentene and Nickelene chloride, wherein isobutylene, 2,3-dimethyl-butene and 2,4,4-trimethyl-1-pentene are preferred. The earthy diene compound can be exemplified as: , 3-butadiene, I, 4-pentadiene, 丨5_ hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, 2 5_ Borneadiene, dicyclopentadiene, 5_Bxian I norbornene, 5 propyl-2-norbornene, 4-vinyl-1-cyclohexene, and 5_Asian Borneene, in which U-pentadiene, -hexadiene, 2,5_ drop; sheet II 321925 23 201041645 ^ene, mono-pentylene, 5-vinyl-2, norbornene, 4_ethylene The base 4-cyclohexanium and 5-ethylidene-2-norbornate are more preferred. The aliphatic Lai B (4) is published, such as ethylene citrate, vinyl propionate, and ethyl butyrate; For example, methyl ether ether Ethyl (10) _ and ethane _ ° _ ethylene can be exemplified by: gas acetylene; cyano vinyl compounds can be exemplified by: acrylonitrile and mercapto acrylonitrile. The polymer CB-υ derived from the addition The enthalpy of the structural unit of the polymerized monomer, such as the amount of adhesion of the cured product obtained by drying the aqueous emulsion of the present invention, can be 'relatively relative to the total structural unit 100 constituting the polymer, 5 moles are better, and alpha i moles are better. • The polymer (B-1) can be produced, for example, by using a transition metal compound having a sulfhydryl anion skeleton or a crosslinked cyclopentadienyl anion skeleton as a catalyst, by polymerizing the corresponding monomer. . The method of the Japanese Patent Publication No. 2003-82028, the Japanese Patent Application Laid-Open No. Hei. No. Hei. ◎In the manufacture of bismuth polymer (B-1), ethylene homopolymer, homopolymer and/or vinyl may be formed depending on the type of catalyst used and the polymerization conditions 'other than polymer'. A homopolymer of cyclohexane. In this case, the polymer (B-1) can be easily taken out by extracting the solvent using a soxhlet extractor or the like. When toluene is used as a solvent, a homopolymer of vinylcyclohexane as an insoluble component can be removed. When chloroform is used as a solvent, a homopolymer of an olefin such as a homopolymer of ethylene which is an insoluble component or a homopolymer of propylene is removed. The polymer (B-1) can be isolated as the coluene component of the solvents. If there is no problem in its use, it is also possible to use a polymer (Β-l) having 24 321925 201041645 as a by-product as described above. The molecular weight distribution of the polymer (B-1) (Mw / Mn = [weight average molecular weight] / [number average molecular weight]) is generally 1.5 to 10. About 〇, the aqueous emulsion of the present invention is hardened by drying. 5至优选。 Preferably, it is preferably from about 1.5 to about 5.0. The weight average molecular weight (Mw) of the polymer (Β-1) is generally from about 5,000 to about 10,000 000, and the mechanical strength of the cured product obtained by drying the aqueous emulsion of the present invention and the polymer (B_i) From the viewpoint of liquidity, it is preferably about 10,000 to 500, and about 1,500 to 400,000. More preferably. The molecular weight distribution of the polymer (Β-1) can be determined by gel permeation chromatography (GPC). The ultimate viscosity [η ] of the polymer (Β-l) is generally from about 0·25 to about 10 dl/g, from the viewpoint of the mechanical strength of the cured product obtained by drying the aqueous emulsion of the present invention. 'It is preferably about 0.3 to 3 dl/g. Melt flow rate of polymer (Bi) measured under conditions of 19 (TC, 2.16 kgf) using a melt indexer (L217-E14011; manufactured by techno7) according to JIS K 7210 The value of the ruler) is usually from 130 to 300 g/l min, preferably from about 10 minutes to about _ minutes from the viewpoint of dispersibility of the polymer (Β-1) in the aqueous emulsion of the present invention. (B-2) means a polymer obtained by graft-polymerizing a non-unsaturated carboxylic anhydride with a polymer (Β-1). 321925 25 201041645, Graft polymerization amount of α, /3 - unsaturated carboxylic anhydride至约约重量重量左右。 Preferably, about 0.1 to 20 parts by weight, preferably from about 0.1 to about 5 parts by weight, more preferably from about 0.1 to about 5 parts by weight, more preferably from about 0.1 to about 5 parts by weight, based on 100 parts by weight of the polymer (Β-2). The aqueous emulsion of the present invention containing the polymer of the α,/3-unsaturated carboxylic anhydride having a graft polymerization amount of 0.01 parts by weight or more (Β-2) preferably has a tendency to improve the adhesion. An aqueous emulsion of the present invention in which the graft polymerization amount of the lu-unsaturated carboxylic anhydride is 20% by weight or less based on the polymer (B-2), due to the heat ν/α, cold-unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, etc., having 4 to 20 carbon atoms, /3-unsaturated carboxylic acid The acid anhydride is preferably maleic anhydride. Two or more kinds of α, /5-unsaturated carboxylic anhydrides may be used in combination. The polymer (Β-2) may be produced by, for example, the following method: (Β-1) a method of adding α, an unsaturated carboxylic anhydride and graft-polymerizing a molten polymer (Β-1) obtained by melting; or dissolving a polymer in a q solvent such as toluene or dioxane (B-1), a method of adding α, hydrazine-unsaturated carboxylic anhydride to a solution obtained by graft polymerization, etc. Graft polymerization is generally carried out in the presence of a radical initiator. When the amount of the starting agent used is small, the amount of graft polymerization of α,β-unsaturated carboxylic anhydride is small, and the cured product obtained by drying the aqueous emulsion of the present invention tends to have difficulty in improving adhesion, and when used in a large amount The amount of unreacted radical initiator contained in the polymer (Β-2) tends to increase, and therefore, relative to the polymerization The compound (Β-1) is 100 parts by weight, generally 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight. 26 321925 201041645 Free radical initiator generally allows the timing to be used at the solution temperature In the case of an organic peroxide of 50 ° C or more, the amount of graft polymerization of ruthenium-non-needle tends to increase, and the polymer in the graft polymerization is used when an organic peroxide at a decomposition temperature of two is used. -1) The tendency of two. After decomposing to generate free radicals, it is preferred to have an organic peroxide having a function of extracting protons from the mouth.

^ / The decay time becomes 1 minute, the decomposition temperature is 50 to 210 Χ: the organic over m can be, for example, 35 bismuth oxy compound, peroxydialkylation port = peroxy ketal compound, alkyl peroxyester The compound and the percarbon 1 曰 ° ° A ' are preferably a peroxo-filament compound, a peroxydicarbonate &amp; carbonated vinegar compound, and a mercapto peroxide vinegar compound. Specific examples thereof include: diperoxide dicarbonate (16 (four)), peroxidized two-plate 1-(3-methoxybutyl), di(2-ethylhexyl) peroxydicarbonate, peroxidation - bis(4-tert-butylcyclohexylglycolate), diisopropyl sulfonate, butyl peroxy isopropyl carbonate, oxidized dimethicone, oxidized neodecanoic acid 1, 1,3, 3-tetramethylbutyl ester, peroxy neodecanoic acid α isopropyl hydrazine, peroxy neodecanoic acid tert-butyl ester, 1,1-bis(t-butylperoxide) hexane , 2, 2-bis(4,4-di-t-butylperoxycyclohexyl)propane bis(butylated butyl peroxide) cyclododecane, isopropyl sulphide monolithic succinct The purpose of peroxidation of '3,5,5-tridecylhexanoic acid, third vinegar, peroxidized laurel H&quot;1&quot;®, 2, 5-dimethyl-2, 5-double (peroxide benzoate) Hexane, oxidized acetic acid tert-butyl ester, 2, 2_bis(t-butylperoxy)butyl hydrazine, benzoic acid benzoic acid, third butyl s, 4, 4- bis (perbutyl tributyl peroxide)戊27 321925 201041645, butyl acrylate, iso-isophthalic acid di(tributyl acrylate), Dicumyl, α,α-bis(t-butylperoxyisopropylidene)benzene, 2,5-dimethyl-2'5-bis(t-butylperoxy)hexane, hydrazine , 3_bis(t-butylperoxyisopropyl)benzene, tributylisopropyl peroxide, dibutylbutyl peroxide, argon peroxide, pnenthane hydroperoxide, and 2, 5 - Dimethyl-2, 5-bis(t-butylperoxy)_3-hexyne. The amount of the organic peroxide added is usually from 0.1 to 20 parts by weight, preferably from 0.1 to 10 parts by weight, based on 1 part by weight of the polymer (8 Å). k can be melt-kneaded using an extruder, and can be used to make a polymer (Β_υ) from the viewpoint of various methods of mixing a plurality of polymers or a polymer with a solid or liquid additive. It is preferred to add α, a point-unsaturated carboxylic anhydride to the molten polymer (Β-1) to carry out graft polymerization, and to combine all or part of the components for graft polymerization. Mixing with a Henschel mixer, a belt mixer, a mixer, etc. to obtain a homogeneous mixture, and then melting and kneading the mixture is more preferable. The means of melt-kneading can be widely used. Bianbury mixer, Brass extruder (?1&amp;31;〇11^11), plastic spectrometer (31^1:^1:1 (^1'?1 shape) VII § 1 ^ this), uniaxial or biaxial extruder specializing in the mixing method. From the viewpoint of continuous production of polymer (B-1) to improve productivity, the polymer ( B-1), a mixture of vermiculite-unsaturated carboxylic anhydride and a radical initiator which are sufficiently mixed in advance, from uniaxial or biaxial The method of supplying and kneading the supply port of the extruder is preferred. The temperature of the portion where the extruder is melt-kneaded (for example, the cylinder temperature of the extruder 32192s 28 201041645) is generally 50 to 300 ° C. It is preferably 80 to 270 ° C. When the temperature is 50 ° C or higher, the graft amount tends to increase, and when the temperature is 300 ° C or lower, the decomposition of the polymer (B-1) tends to be suppressed. The smelting time is generally from 0.1 to 30 minutes, and the temperature is preferably from 0.1 to 30 minutes, so that the temperature of the melt-kneading in the second stage is higher than the temperature of the melt-kneading in the first stage. 0. 1 to 5 minutes is preferred. When the melt-kneading time is 0.1 minutes or more, the graft amount tends to increase, and when the melt-kneading time is 30 minutes or less, the decomposition of the polymer (B-1) There is a tendency to be suppressed. The structural unit derived from α, cold-unsaturated carboxylic anhydride in the polymer (B-2) may be a structural unit for maintaining an acid anhydride structure, or may be an open-loop structure derived from an acid anhydride structure. The structural unit of the /3-unsaturated carboxylic acid may also be a structure containing both a maintenance anhydride structure And the molecular weight distribution (Mw/Mn) of the polymer (Β-2) is generally 1.5 to 10, in terms of a molecular weight distribution (Mw/Mn) of the polymer (Β-2). 1. 5 to 7 is preferable, more preferably 1.5 to 5. The molecular weight distribution of the polymer (B-2) can be measured in the same manner as the molecular weight distribution of the above polymer (B-1).至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至至3dl/g is better. The melt flow rate (MFR) of the polymer (B-2) measured at 190 ° C, 2.16 kgf using a melt indexer (L217-E14011; manufactured by techno7) according to JIS K 7210 The value is generally 29 321925 201041645 130 g/10 minutes or more and 300 g/10 minutes or less, and is 130 g/10 minutes or more and 200 g from the viewpoint of dispersibility of the polymer (B-2) in the aqueous emulsion of the present invention. Below /10 minutes is preferred. The aqueous emulsion of the present invention contains water as the component (C) in addition to the component (A) and the component (B), and the component (A) and the component (B) are dispersed, and the component (C) ) is an emulsion of a dispersion medium. The volume reference median diameter of the dispersoid is generally from 〇.〇l/zm to 3//m, preferably from 0.1/zm to 2/ζιη, preferably from 0.5/zm to more preferably. When the volume-based median diameter is 0.01/m or more, the aqueous emulsion is easy to manufacture. For example, when it is 3/im or less, the static stability of the aqueous emulsion and the adhesion of the cured product obtained by drying the aqueous emulsion are The tendency to improve. "Stabilization stability" means that the aqueous emulsion is uniform when it is kept for 3 days without being stirred, that is, it is difficult to form a component in the aqueous emulsion (B), and the layer and/or the component (C) is rich. The nature of the layer. The "volume-based median diameter" means that the value of the cumulative particle size distribution corresponds to 50% of the particle diameter on a volume basis. The content of the component (A) in the aqueous emulsion of the present invention is usually from 1 to 30 parts by weight, preferably from 2 to 10 parts by weight, per 100 parts by weight of the (B). The total content of the component (A) and the component (B) in the aqueous emulsion of the present invention is generally 10 to 90 parts by weight, preferably 30 to 70 parts by weight, and preferably 40 to 60 parts by weight based on 100 parts by weight of the aqueous emulsion. Better. The content of the component (C) in the aqueous emulsion of the present invention is usually 90 to 10 parts by weight, preferably 70 to 30 parts by weight, more preferably 60 to 40 parts by weight, per 100 parts by weight of the aqueous emulsion. 30 321925 201041645 The aqueous emulsion of the present invention may, for example, be a method in which the obtained molten mixture is mixed with water after melt-kneading the component (A) and the component (B); and the component (A) is mixed with the heated component. (B) the method of the step; the component (A) - and the component (B), after heating and kneading, dispersing the obtained kneaded mixture in the component (C); and containing the component (B) After the organic solvent such as toluene, the obtained solution is mixed with the component (A), and the step of removing the organic solvent from the obtained mixture is carried out. In addition, chemical emulsification methods such as self-emulsification can also be used. In the above, the method in which the component (A) and the component (B) are melt-kneaded, and the obtained molten mixture is mixed with water, and the step of mixing the component (A) into the component (B) of the addition-heating The method is suitable. The apparatus used in the step of melt-kneading the component (A) and the component (B) may be, for example, a twin-screw extruder or an experimental-stage Brass extruder (labo plast mill; Toyo Seiki Co., Ltd.) ) Manufacturing), micro-experimental Brass extruder (labo plast mill micro; manufactured by Toyo Seiki Co., Ltd. Q) and other multi-axis extruders; homogenizer, TK FILMIX (primix) (manufacturing), etc. Machines with barrels; cylinders, chemical mixers, vortex mixers, jet jet mixers, colloid mills, ultrasonic generators, high pressure homogenizers , such as a machine that does not have a barrel (cylinder), such as a static mixer (a registered trademark of Fujitsu Co., Ltd.), a static mixer, or a micro-mixer. The shear rate of a machine having a barrel is generally from 200 to 100,000 seconds _1, preferably from about 1000 to 2500 sec-1. When the shear rate is 200 sec or more, the cured product obtained by drying the aqueous emulsion has an improved adhesion. 31 321 925 201041645. If it is 100000 sec or less, the aqueous emulsion tends to be industrially easy to manufacture. "Shear rate" means the value obtained by dividing the circumferential speed [mm/sec] of the outermost portion of the screw member by the gap [mm] between the screw and the barrel. - A method of melt-kneading the component (A) and the component (B), for example, continuously supplying the component (B) from a hopper or a supply port of a biaxial press, and performing the component (B) Heating and melt-kneading, and supplying the component (A) to at least one supply port installed in the compression zone, the metering zone or the degassing zone of the extruder, and then performing the component (A) and the component (B) The kneading is followed by a method in which the component (C) is supplied from at least one supply port in the compression zone of the extruder, whereby the aqueous emulsion is continuously extruded from a die. The method including the step of mixing the component (A) into the heated component (B), for example, after heating the cylinder of the kneader, the component (B) is placed in the cylinder and rotated while being rotated. Further, the component (B) is melted, and then the component (A) is charged, and the component (A) and the component (B) are mixed while being rotated, and the resulting mixture is poured into warm water to thereby cause the component (A) and Component (B) Q A method in which the component (C) is dispersed to obtain an aqueous emulsion. The method comprising the step of mixing the component (A) into the heated component (B) is preferably a method using a multiaxial extruder. Specifically, first, the component (B) is supplied from a hopper of a multi-axis extruder having two or more screws in a tank, and the component (B) is heated and melted and kneaded, and secondly, it is installed in the extrusion. At least one liquid supply port of the compression zone of the press and/or at least one liquid supply port of the metering zone is supplied with the component (A), and the component (A) and the component (B) are kneaded and dispersed in the component (C). The aqueous emulsion of the present invention may contain: an aqueous polyurethane emulsion, ethylene-32 321925 201041645 vinyl acetate copolymer aqueous emulsion and other aqueous emulsions; thermosetting resin such as urea resin, melamine resin, phenol (Phenol) resin; clay Filling agent such as sorghum, talc, calcium carbonate; preservative; rust preventive; defoaming door foaming agent; polyacrylic acid, polyacrylic acid, methyl cellulose, dimethomethyl fiber, 'polyvinyl alcohol, starch Such as tackifiers; viscosity modifiers; flame retardants; pigments such as titanium oxide; humic acid dimethyl vinegar, adipic acid dimethyl and other high boiling solvents 丨 = chemicals. , Ο

G: By drying the aqueous emulsion of the present invention, it is possible to obtain a cured product excellent in adhesion to wood materials, cellulose materials, plastic materials, ceramic materials, and metal materials. The drying temperature is generally from 3 () to 乂 60 to 150 C. The drying time is generally from 1 minute to 12 hours, preferably from 10 minutes to 6 hours. Drying can be carried out under ventilation and left under reduced pressure. The cured product of the present invention is excellent even when it is dried at a low temperature of (10) U right. In addition, the cured product obtained by drying the water I and the raw emulsion has excellent adhesion properties even when it is difficult to form a hydrocarbon (for example, a feedstock) with a material such as a coating material. By coating the aqueous emulsion of the present invention on a substrate, a laminate in which the aqueous emulsion layer is laminated on the substrate can be obtained, and by drying the laminate, the substrate layer and the cured product can be formed. The layered body of the layer formed. The layer composed of the cured product can be used as a paint, a money, a substrate, a squeegee or the like. The substrate may be any one which can coat the aqueous emulsion of the present invention, and may have any shape. ... The substrate can be listed as: wood, plywood, MDFOnedium density 321925 33 201041645 'fiberboard, medium density fiberboard), particle board, fiberboard and other wooden materials; paper, wrapping paper and other paper materials; cotton, linen, snail Cellulose material such as rayon; polyethylene (contained from acetamidine, polyolefin based on the unit, the same as below), polypropylene (polyolefin based on structural units derived from propylene) , the same as below), polyolefin such as polystyrene; polycarbonate, acrylonitrile/butadiene/styrene copolymer (ABS resin), (meth)acrylic resin polyester, polyether, polyvinyl chloride, polyurethane , plastic materials such as foaming amine ester; ceramic materials such as glass and ceramics; and metal materials such as iron, tantalum stainless steel, copper and aluminum. The substrate can be a composite of a plurality of materials. It can also be an inorganic filler such as talc, cerium oxide or activated carbon, or a mixture of carbon fiber and other plastic materials. Here, the polymer in which the polyurethane is crosslinked via an amine ester bond is generally obtained by a reaction of an alcohol (a compound having -OH) with an isocyanate (a compound having -NC0). The foamed polyurethane is a polyurethane which is foamed by a volatile solvent such as carbon dioxide or Freon which is produced by the reaction of isocyanate with water as a crosslinking agent q. The interior components of automobiles are generally made of semi-rigid polyurethane, and the coatings are generally made of rigid polyurethane. Among the substrates, polypropylene, polystyrene, polycarbonate, acrylonitrile/butadiene/styrene copolymer (ABS resin), polyethylene terephthalate, polyethylene, (methyl) Acrylic resins, glass, aluminum, and polyurethane are preferred, and polypropylene, polyethylene, glass, aluminum, and polyurethane are more preferred. The cured product obtained from the emulsion of the present invention can be used as a substrate for carrying out two types of substrates. When the substrate on one side is a water-absorbent substrate such as a wood material, a paper material 34 321 925 201041645 material, or a cellulose material, if the aqueous emulsion of the present invention is applied to the water-absorbent substrate, the aqueous emulsion contains The component (c) is absorbed by the water-absorptive substrate, and an adhesive layer containing the component (A) and the component (B) is formed on the water-absorbent substrate. Therefore, a laminate obtained by laminating the water-absorbent substrate, the adhesive layer, and the other substrate in this order can be obtained by bonding the other substrate to the adhesive layer. When the substrate on one side is a non-absorbent substrate such as polyolefin, the aqueous emulsion of the present invention is applied onto the non-absorbent substrate, and then heated to form a hardened layer on the non-absorbent substrate. Then, the other side of the substrate is bonded to the cured product, and then the laminate is obtained by heating. The heating temperature is usually 60 to 200 °C. The aqueous emulsion of the present invention can impart a cured product excellent in adhesion even when the heating temperature is 60 to 90 ° C, and can provide a cured product excellent in adhesion even at a low temperature of 65 to 80 ° C. . For the cured product of the present invention, the liquid material can be further applied as a coating material. The coating material may, for example, be a material of the above-mentioned base material such as polyamine S. If it is a liquid material, it is excellent in adhesion to the cured material. (Embodiment) Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. [Solid fraction] The solid fraction was measured in accordance with the method of JIS K-6828. [Molecular Weight and Molecular Weight Distribution] The molecular weight of the component (B) was measured by gel permeation chromatography (GPC). 35 321925 201041645 Calibration with polystyrene (molecular weight 688 to 400,000) reference material and obtained under the following conditions. Meanwhile, the molecular weight distribution is evaluated in a ratio (Mw/Mn) of a weight average molecular weight (hereinafter referred to as Mw) with respect to a number average molecular weight (hereinafter referred to as Μη).

Model Waters System 150-C

Column shodex packed column A-80M

Measuring temperature 140 ° C Determination of solvent o-dichlorobenzene

Determination of concentration lmg/ml [NH3 neutralization degree] The NH3 neutralization degree of the emulsifier means the molar number of the structural unit derived from acrylic acid relative to the component (A) contained in the emulsifier and the succinic acid-derived 2- The total number of moles of the structural unit of the mercaptopropenyloxyethyl ester is represented by the molar ratio (%) of the ammonia used. Here, the number of moles of each structural unit is assumed to be the same as the number of moles of each monomer used in the production of the component (A). [Content of structural unit derived from vinylcyclohexane] The content of the structural unit derived from vinylcyclohexane in the component (B) means that the 13C-Li spectrum of the component (B) is based on the following conditions The measured result was calculated based on the following formula (X). 13C-NMR device: DRX600 manufactured by BRUKER Co., Ltd. Solvent: A mixture of o-dibenzene and o-diphenyl-d4 in a ratio of 4:1 (volume ratio)

Measurement temperature: 135 ° C Measurement method: Powergate Decouping pulse angle: 45 degrees 36 321925 201041645 'Base of measurement: Tetramethyl decane derived from the content of structural units of vinyl cyclohexane (mo 1 %) = 100xA / ( B-2A) (X) (In the formula (1), A represents an integral cumulative value of a signal of 45 ppm to 40 ppm, and B. represents an integrated integrated value of a signal of 35 ppm to 25 ppm). [Graft amount] The graft amount of maleic acid if in the component (B) was determined by the following operation. 〇 (i) The sample solution was prepared by dissolving the sample 1. 〇g in 20 ml of xylene. (ii) The prepared solution was added dropwise to 300 ml of decyl alcohol while stirring. (iii) The precipitate precipitated from the sterol was recovered and dried at 80 ° C for 8 hours. (iv) A film having a thickness of 100/zm was produced by hot pressing using a dried solid. (v) The infrared absorption spectrum of the produced film was measured, and the graft amount of maleic acid was quantified based on the absorption peak near 1780 CHT1. 〇[limit viscosity] The ultimate viscosity of component (B) ([7/ ]; unit: dl/g) is determined by using Ubbelohde type viscometer with tetrahydronaphthalene as solvent at 135 °C. . [Glass conversion temperature and melting point] The glass transition temperature ([Tg]; unit: °C) of the component (B) and the melting point ([Tin]; unit: °C) are using a differential scanning calorimeter (Seiko Electronics Industry) The company's manufacturing, SSC-5200), measured the differential scanning calorimetry curve under the following conditions, and obtained the differential scanning calorimetry curve obtained in the step (c). 37 321925 201041645, <Measurement conditions> (a) The sample was heated from 20 ° C to 200 ° C at 10 ° C / min, and then maintained at 200 ° C for 10 minutes.

(b) The sample obtained in (a) was cooled from 200 ° C to -100 ° C at 10 ° C / min, and maintained at -100 ° C for 10 minutes. (c) The sample obtained in (b) was heated from -100 ° C to 200 ° C at 10 ° C / min. The single system of the derived structural unit (al) is made of acrylic acid (Mitsubishi Chemical Co., Ltd., hereinafter referred to as AA); the single system of the derived structural unit (a2) is used ^ N,N-diamine-based methacrylate Ester (manufactured by Sanyo Chemical Industry Co., Ltd., hereinafter referred to as DMA); the single system of the derivatized structural unit (bl) uses decyl decyl acrylate (Mitsubishi snail (manufactured by Miki), hereinafter referred to as 匪A), methyl Lauryl acrylate (Mitsubishi snail (manufactured by the company), hereinafter referred to as LMA) and decyl decyl acrylate (Mitsubishi snail (manufactured), hereinafter referred to as TDMA); derived structural unit (b3) single system use 2-Methyl propylene methoxyethyl succinate (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter abbreviated as H0-MS) to produce the q component (A). In addition, "parts" and "Γ" in the following examples are based on the weight limit. <Production Example 1 of the component (A)> AA 24. 5 parts (42. 3 molar ratio), HO -MS 22. 5 parts (12. 2 mole ratio), DMA 28. 0 parts (22. 2 mole ratio), MM 15. 0 parts (18.6 mole ratio), LMA 3. 8 parts (1.8 Mohrby) and TDMA 6.2 parts (2.9 mole ratio) are mixed at 10 to 30 ° C to prepare 100 parts of the monomer mixture. Here, "Morby" means the total number of moles of the above monomers. The number of moles of each monomer at 100. 38 321925 201041645 150 parts of isopropanol and ions were fed into a 1 L reactor equipped with a heating jacket with a condenser, a nitrogen inlet tube, a stirrer, and a dropping funnel. 100 parts of water were exchanged, and while the obtained solution was stirred, the internal temperature was adjusted to 80 ° C. After the gas in the reaction vessel was replaced with nitrogen, 20 parts of the monomer mixture prepared above was added at once. 2 parts of 2, 2'-azobisisobutyronitrile as a polymerization initiator, and the resulting mixture was stirred at 80 ° C. Then, at 80 ° C, the fee was charged.份份份。 2, 2'-azobisisobutyronitrile 0. 15 parts, every 1 hour, from the beginning of the dropwise addition, the mixture of the mixture was added to the mixture. The mixture was added in four portions. The resulting mixture was stirred at the same temperature for 3 hours. The resulting reaction was mixed and heated to a boiling degree to distill off the isopropanol. After the internal temperature of the obtained concentrate was cooled to 50 ° C, the mixture was mixed. % of aqueous ammonia solution 39. 9 parts (81. 7 mole ratio, the molar ratio of ammonia when the total number of moles of the above monomers is 100), to obtain acrylic acid containing a polymer hydrophilic ratio of 9.40. A viscous emulsifier having a degree of neutralization of 150%, and a yield of 90%. The obtained emulsifier is referred to as hydrazine (A-1). The results are shown in Table 1. <Production Examples 2 to 4 of Component (A) The same operation as in Production Example 1 of the above component (A) was carried out except that the type and amount of the monomer to be used and the amount of use of the ammonia were changed as shown in Table 1, and a viscous emulsified product containing an acrylic resin was obtained. The obtained emulsifiers are referred to as (A-2), (A-3) and (A-4), respectively, and the results are presented in the table. 39 321925 201041645, [Table 1] Production Example 1 Production Example 2 Production Example 3 Production Example 4 (A-1) (A-2) (A-3) (A-4) Parts Mo Erbi Mo Mobi Ear ratio molar ratio monomer AA 24. 5 42. 3 34. 5 54. 5 34. 5 54. 5 49. 5 69. 3 H0-MS 22. 5 12. 2 22. 5 11. 1 22. 5 11. 1 22. 5 9. 9 DMA 28. 0 22. 2 18. 0 13. 0 18. 0 13. 0 3. 0 1.9 ΜΜΛ 15. 0 18. 6 15.0 17.1 15. 0 17. 1 15. 0 15· 1 LMA 3. 8 1.8 3.8 1.6 3. 8 1.6 3. 8 1.4 TDMA 6. 2 2. 9 6. 2 2. 7 6. 2 2. 7 6. 2 2.4 Total 100 100 100 100 100 100 100 100 NHa usage (Mo Erbi) 81.7 98.4 78. 7 95 • 0 NH3 application (3⁄4) 150 150 120 120 Monomer hydrophilic ratio 9.40 9. 91 9. 91 10. 68 <Manufacture of component (B) 1&gt; After replacing the internal gas of the stainless steel reactor with argon gas, 386 parts of vinylcyclohexane and 3640 parts of toluene were charged therein. After the resulting mixture was warmed to 50 C, ethylene was fed into the reactor while being pressurized at a pressure of 66 MPa. Further, a toluene solution of triisobutylammonium (manufactured by Tosoh Akzo Corporation; 20% by weight) was added, and then, by using diethyl decyl (tetramethylcyclopentane) a solution of a dienyl)(3_t-butyl-5-fluorenyl-2-phenoxy)titanium dichloride 001 solution dissolved in 87 parts of dehydrated toluene, and by dimethylanilide Tetrakis(pentafluorophenyl)borate 0.03 parts of a solution obtained by dissolving 122 parts of dehydrated toluene was fed into the reactor. The resulting mixture was stirred for 2 hours. The resulting reaction mixture was poured into about 10,000 parts of acetone, and the precipitated white solid was taken out by filtration. The solid which was taken out was washed with acetone and dried under reduced pressure to give 300 parts of ethylene-vinyl 321925 40 201041645 cyclohexane copolymer. The obtained copolymer had [π] of 0.48 dl/g; Μη was 15,600; Mw/Mn was 2; Tm was 57 ° C; Tg was -28 ° C; and structural units derived from vinylcyclohexane The content rate was 13 mol%. The resulting copolymer is referred to as (B-1 a). <Production Example 2 of Component (B)> 0.4 parts of maleic anhydride and 0.04 parts of 1,3-bis(t-butylperoxyisopropyl)benzene were added to 100 parts of (B-la), and the obtained mixture was sufficiently Stir and prepare for mixing. The resulting mixture was supplied from a supply port of a twin-screw extruder and melt-kneaded. At the same time, the melt-kneading is carried out in two stages of the first half and the second half, and the temperature of the first half of the portion in which the extruder is melt-kneaded is set to 180 ° C, and the temperature of the second half is set to 260 ° C. Then, melt kneading is carried out. As a result, a copolymer obtained by graft-polymerizing an ethylene-vinylcyclohexane copolymer with maleic anhydride was obtained. 2%; MFR was 180 g/10 min (190 ° C; load: 2.16 kgf). The resulting copolymer is referred to as (B-2a). <Production Example 3 of the component (B)> In the production example 1 of the component (B), the same operation as in the production example 1 of the component (B) was carried out, except that propylene was used instead of ethylene, to obtain propylene-ethylene. A cyclohexane copolymer. This copolymer is referred to as (B-lb). <Production Example 4 of the component (B)> In the production example 2 of the component (B), the production example 2 of the component (B) is carried out except that the (B-lb) substitution (B-la) is used. In the same manner, a copolymer obtained by graft-polymerizing a propylene-vinylcyclohexane copolymer with maleic anhydride was obtained. This copolymer is referred to as (B-2b). 41 321925 201041645, Example 1 The cylinder temperature of the table kneading machine ρβνυ type (purchased from the Jinjiang Chamber of Commerce) was set to 97. (: After 'injection (B-2a) 110 parts in the cylinder, and rotate clockwise by 1 minute per minute.] (B-2a) melts in 10 minutes. Then, the solid component becomes The amount of (A-1) was 10 parts per minute, and the glass lid was opened from time to time, and the mixture was emulsified for 3 minutes. Then, 9 parts of warm water of TC was added to obtain an aqueous emulsion. The volume-based median diameter of the dispersoid in the obtained aqueous emulsion is 〇1.3 from m. The volume-based median direct enthalpy is produced by a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, Ltd.) The adhesion of the cured product obtained from the aqueous emulsion was evaluated by the following test method (checkerboard tape peeling method). The results are shown in Table 2. Further, the appearance of the obtained aqueous emulsion after storage for 3 days without stirring was observed. There is no change in the uniformity of the sentence, and the static stability is also good. <Test method for adhesion> 〇 = thickness 3_ The surface of the plate (4) is washed with isopropyl alcohol and then coated on the polypropylene board with an emulsion. , to make the hard r after drying, 5 Ί", 1G / / m. The air dryer dries the obtained coating film at 8 (rc), and then dried and dried in a 7GC oven towel for 30 minutes to obtain a coating rod of a polypropylene plate having a thickness of 3 mm. After the cleaning of the propanol, the thickness of the compound film was changed to 10//^, and the hardened film was dried to a hardness of 5 Å to 'm", and the air dryer was used to obtain the coating film at 8 (TC). The oven was heated and dried for 30 minutes to obtain a cured product of 321925 42 201041645. Based on JIS-K5400 (checkerboard tape peeling test), a checker-shaped cut with a gap interval of 1 mm was applied to each of the obtained cured products. After that, the scotch tape was attached thereto. After 1 to 2 minutes, the glue was attached. • The tape was peeled off at a right angle, and the adhesion was evaluated according to the following evaluation criteria. ◎: No peeling of the cured product was observed. 〇: Although peeling of the cured product was observed, the peeling area was less than 40% of the square area. 〇X: peeling of the cured product was observed, and the peeling area was 40% or more of the square area. Example 2 will be in the same direction Rotating meshing twin screw extruder (Day Steelmaking (stock) manufacturing: ΤΕΧ30Φ; L/D=30) After the cylinder temperature is set to 110 °C, 110 parts of (B-2a) are continuously and continuously from the feeding hopper of the weaving machine at a screw rotation number of 35Orpm. It is supplied to the inside of the cylinder. From the supply port of the venting portion of the venting portion of the ejector, the gear member is pressurized, and the solid component is continuously supplied in an amount of 10 parts (A-1). And the volume-based median diameter of the dispersion of the obtained aqueous emulsion is 1. 0 Am. The volume-based median diameter was measured by a laser diffraction/scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd.). The adhesion of the cured product obtained from the aqueous emulsion was evaluated by the test method described in Example 1. The results are presented in Table 2. Example 3 43 321925 201041645 In Example 1, except that (A-1) was substituted for (A-1), the same operation as in Example 1 was carried out to obtain a milky white aqueous emulsion. After the obtained aqueous emulsion was stored for 3 days without stirring, its appearance and uniformity did not change, and the standing stability was also good. The evaluation results of the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the adhesion of the cured product obtained from the aqueous emulsion are shown in Table 2 ° Example 4 ^ Example 1, except (A-3 The same operation as in Example 1 was carried out, except for (A-1), to obtain a milky white aqueous emulsion. After the obtained aqueous emulsion was stored for 3 days without stirring, its appearance and uniformity did not change, and the standing stability was also good. The results of the evaluation of the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the adhesion of the cured product obtained from the aqueous emulsion are shown in Table 2 ° Q Example 5, except that (A-4) The same operation as in Example 1 was carried out, except for (A-1), to obtain a milky white aqueous emulsion. After the obtained aqueous emulsion was stored for 3 days without stirring, its appearance and uniformity did not change, and the standing stability was also good. The results of the evaluation of the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the adhesion of the cured product obtained from the aqueous emulsion are shown in Table 2. 44 321925 201041645 ο

Example 6 In Example 2, except that (B_la) was substituted (B_2a), the same operation as in Example 2 was carried out, whereby an aqueous emulsion was obtained. In Example 7, the same procedure as in Example 2 was carried out except that (B-lb) was used instead of (B-2a), whereby an aqueous emulsion was obtained. Example 8 In Example 2, an aqueous emulsion was obtained by the same operation as in Example 2 except that (B_2b) was used instead of (B-2a). [Industrial Applicability] The aqueous ritual agent of the present invention can provide a cured product which is excellent in adhesion to a substrate which is difficult to adhere to a material such as a polypropylene material. [Simple diagram description] No 0 321925 45 201041645 [Main component symbol description]

Claims (1)

201041645 VII. Scope of application: 1. An aqueous emulsion containing the following components (A), (β) and (C): Ingredients (Α): Contains α, s-unsaturated carboxylic acid a structural unit, and a structural unit derived from a fluorinated aliphatic alcohol having a carbon atom number of 1 to 1 Å having a substituent and an a, unsaturated carboxylic acid derived from an α-unsaturated carboxylic acid Acrylic resin, wherein the acrylic acid The hydrophilic ratio of the resin is from 9 to 12 (here, the hydrophilic ratio of the acrylic resin is the weight average of the hydrophilic ratio of the monomer from which the structural unit of the acrylic resin is derived, and the hydrophilic ratio of the monomer is determined by the following formula Calculated values: # hydrophilic ratio of monomer = 20 χ (the amount of the hydrophilic portion of the monomer) / (molecular weight of the monomer)); composition (Β): thermoplastic polymer; component (C): water. 2. The aqueous emulsion of claim i, wherein the component (8) comprises: a thermoplastic polymer having a structural unit derived from ethylene and/or propylene. 3.=Please refer to the water content of the third paragraph of the patent (4), wherein the (8) component is contained in the structural unit derived from ethylene and/or (4) and is derived from the formula (I) (I) CH2=CH-R , R represents a copolymer of a structural unit of a compound of a 2-stage alkyl group, a 3-stage alkyl group or an alicyclic hydrocarbon group, and is obtained by graft polymerization of a carboxylic acid anhydride of 321925 47 201041645 . 4. The aqueous emulsion according to item 3 of the patent application, wherein the vinyl compound represented by the formula (I) is an ethylene ring cyclohexene. 5. The aqueous emulsion according to any one of claims 1 to 4, wherein the component (B) is a thermoplastic having an MFR (190 ° C, 2.16 kgf) of 130 g/10 min or more and 300 g/10 min or less. polymer. 6. The aqueous emulsion according to any one of claims 1 to 5, wherein the aqueous emulsion is characterized in that the component (A) and the component (B) are dispersed and the component (C) is a dispersion medium. Wherein, the volume-based median diameter of the dispersoid is from 0.01/m to 3/zm. 7. The aqueous emulsion according to any one of claims 1 to 6, wherein the aliphatic alcohol having from 1 to 10 carbon atoms having a substituent-containing amine group is derived from α, /3-unsaturated The structural unit of the α,石-unsaturated carboxylic acid ester derived from the carboxylic acid is a structural unit derived from N,N-diguanylaminoethyl methacrylate. 8. The aqueous emulsion according to any one of claims 1 to 7, wherein the structural unit derived from the α,/3-unsaturated carboxylic acid is a structural unit derived from acrylic acid or mercaptoacrylic acid. A method for producing an aqueous emulsion, characterized in that after the component (Α) and the component (Β) are melt-kneaded, the obtained molten mixture is mixed with water; the component (Α): contains 〇:, /3- a structural unit of a saturated carboxylic acid, and an α,/3-unsaturated acid derived from an aliphatic alcohol having a carbon atom number of 1 to 10 and an α,β-unsaturated carboxylic acid derived from an amine group having a substituent. The acrylic resin of the structural unit of the ester, wherein the hydrophilic ratio of the acrylic 48 321 925 201041645 resin is 9 to 12 (here, the hydrophilic ratio of the acrylic resin is the hydrophilic ratio of the monomer from which the structural unit of the acrylic resin is derived The average weight, the hydrophilic ratio of the monomer is calculated by the following formula: The hydrophilic ratio of the monomer = 20x (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer)); (B): thermoplastic polymer; component (C): water. ❹ 10. A cured product obtained by drying an aqueous emulsion of any one of claims 1 to 8. 11. A laminate comprising: a substrate layer composed of at least one material selected from the group consisting of a wood material, a cellulose material, a plastic material, a ceramic material, and a metal material, and the patent application scope The layer consisting of 10 hardened materials. 12. A method of manufacturing a laminate comprising the steps of: ζ) a base composed of at least one material selected from the group consisting of wood materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. On the material layer, the aqueous emulsion of any one of claims 1 to 8 is coated to obtain a laminate having the substrate layer and the aqueous emulsion layer; and the laminate obtained in the above step is dried to obtain A step of providing a laminate of the above-mentioned base material layer and the cured layer obtained from the above aqueous emulsion. 13. An emulsifier comprising a structure comprising 49,321,925 201041645 units derived from α, /3-unsaturated acid groups, and an aliphatic group having from 1 to 10 carbon atoms derived from a substituentable amine group An alcohol and (2, yS-unsaturated carboxylic acid derived (2, an acrylic resin of a structural unit of a cold-unsaturated carboxylic acid ester as an active ingredient, and the hydrophilic ratio of the acrylic resin is 9 to 12 (in Here, the hydrophilic ratio of the propionic acid-based resin is a weight average of the hydrophilic ratio of the monomer derived from the structural unit of the acrylic resin, and the hydrophilic ratio of the monomer is a value calculated by the following formula: The hydrophilic ratio = 20x (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer). 14. The emulsifier of claim 13, wherein the source is free of a group having an amine group which may have a substituent The &lt;2,/5-unsaturated carboxylic acid structural unit derived from an aliphatic alcohol having 1 to 10 carbon atoms and α, /3 -unsaturated acid is derived from cerium methacrylate, hydrazine-dimethyl The structural unit of the aminoethyl ester. 15. The emulsifier according to claim 13 or 14, wherein The structural unit derived from the cold-unsaturated carboxylic acid is derived from a structural unit selected from at least one selected from the group consisting of acrylic acid and methacrylic acid. 16. The invention of any one of claims 1 to 8 The use of the aqueous emulsion is for forming a hardened layer on a substrate layer composed of at least one material selected from the group consisting of wood materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. 321925 201041645 ^ IV. Designated representative map: There is no schema in this case. (1) The representative representative figure of this case is: ( ). (2) The symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: There is no chemical formula in this case. 321925 201041645 _ 99109034号:Special: 利;t请案丨(终极丨|?2 31 ) ! / ...,,: The structural unit of β-unsaturated carboxylic acid is derived from acrylic acid or ruthenium, acid structure unit. &lt;9&gt; A method for producing an aqueous emulsion, characterized in that the component (A) and the component (B) are melt-kneaded, and the obtained molten mixture is mixed with the component (C); and the component (A): contains the source a structural unit derived from an α,anthracene-unsaturated carboxylic acid, and an aliphatic alcohol derived from an aliphatic alcohol having 1 to 10 carbon atoms having a substituent group and an α,/3-unsaturated carboxylic acid, An acrylic resin having a non-unsaturated carboxylic acid ester structure, wherein the acrylic resin has a hydrophilic ratio of 9 to 12 (herein, the hydrophilic ratio of the acrylic resin is a single unit derived from the structural unit of the acrylic resin) The weight average of the hydrophilic ratio of the body, and the hydrophilic ratio of the monomer is a value calculated by the following formula: The hydrophilic ratio of the early body = 20 χ (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer) ); Ingredients (Β): Thermoplastic polymer; Ingredient (C): Water. The 〇3-type hardened material is obtained by drying the aqueous emulsion described in any one of &lt;1&gt; to &lt;8&gt;. : </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The substrate layer composed of the factory jin and the hardened material described by &lt;1〇&gt; are described in the following steps: In the at least one selected from the group consisting of wood materials, shim materials, and metal materials _中(4)(4)2 321925(Revised Edition) 991〇9〇3&lt;| Patent Application (July 9 2 3曰^ 201041645 'Carboxyphenyl. * 纟 has Lai County's carbon number 1 to H) Aliphatic alcohol and α, Θ 气 和 和 和 和 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Ethyl vinegar, gamma acid, propyl ketone ethoxylate (tetra) and (iv) 2-methyl propyl ethoxy acetate. (The acrylic resin of the b-thin component (A) may contain two or more types of structural unit structural units (10) which are derived from a polycondensed diol and a non-saturated (four) sulphate and a few acid vinegar. Examples of the glycerol-based diol include, for example, polyethylene glycol, propanol, polyethylene glycol, polypropylene glycol, polyethylene glycol polytetramethylene glycol, methoxy polyethylene glycol, etc., which are bonded to each other via an oxygen atom. a poly calcined diol obtained by extruding a carbon and having a number of atoms of 1 to 4, and the end of the polyglycol diol can be reduced by a number of carbon materials to 2G, (4) fluorenyl, fluorenyl propylene fluorene The protection of the base, etc. The α derived from the polyalkylene glycol and the α,stone-unsaturated carboxylic acid, the non-sufficient and the several acid vinegar may be exemplified by: acrylic acid propylene glycol vinegar, acrylic acid polyethylene glycol S , acrylic acid polyethylene glycol polypropylene glycol vinegar, monoacrylic acid polyethylene glycol polytetramethylene glycol vinegar, acrylic acid ethoxylated polyethylene glycol vinegar, methacrylic acid polypropylene glycol vinegar, methyl propyl acrylate Dilute polyethylene glycol vinegar, polyethylene glycol propylene glycol methacrylate, polyethylene glycol polytetramethylene glycol methacrylate and methoxy polyethylene glycol methacrylate The acrylic resin of the component (A) is preferably one containing a structural unit (Μ) or a structural unit (b3), and more preferably a structural unit (bi) and a structural unit (b3). 13 321925 (Revised) Edition) Patent Application No. 1〇9〇34 (July 23, 1999) 201041645 \ (July 9 9 2) All structural units of B1 (B 1) are generally 95 (9) Mohr is preferably (10) to 70 mol, and more preferably 9 〇 to go Mo. • #合(Β-1) may have a structure/unit derived from an addition polymerizable monomer. Addition-polymerized single-system ethylene, (iv), linear hydrocarbons having 4 to 2 carbon atoms, and monomers other than the vinyl compound (1), bismuth and ethylene, propylene, and carbon atoms 4 to 20 Chain olefins and B = left, polymerized monomers' and the number of carbon atoms of the monomer is usually as follows: ring _, formula ((1) 乙 _ compound, gas acetonitrile compound, 酸酸, The above M-unsaturated (tetra) vinegar and the following. 'di = anhydride. α, euunsaturated carboxyl group R·h2c=&lt; (ii) R, r (wherein R and 卩 are independent, meaning the number of carbon atoms is 1 to Key-shaped, branched or cyclic stimuli or south atom.) Straight-ring dilute hydrocarbons can be exemplified by: cyclobutene, ring π 3-methyl ring (tetra) m cyclopentene &amp;, nucleus, rare, rare, HR ice selection 5 - ethyl ^ base; ^, 2 ~ norbornene drop =: stupid i ice...5, base_2; ice butyl: 2-tetranuclear dodecene, 2 three ring eucalyptus Aene, a yin undecene, 2 to 5 ring 15 32! 925 ζ revision) 22 201041645 $ 视 专利 Patent Application No. 34 (July 23, 1999) 'The manufacturing method of the aqueous emulsion of the present invention can be enumerated For example, the component (A) and the component (B) are melt-kneaded and then the method of mixing and mixing the obtained molten mixture with the component (C); comprising mixing the component (A) into the heated component (B) The method of the step 'The component (A) and the component (B) are heated and kneaded, and the obtained kneaded mixture is dispersed in the component (C); and the component (B) is dissolved in an organic solvent such as toluene. Thereafter, the obtained solution is mixed with the component (A), and the step of removing the above organic solvent from the resulting mixture is carried out. In addition, chemical emulsification methods such as self-emulsification can also be used. Here, the method of mixing the obtained molten mixture with the component (C) by melt-kneading the component (A) and the component (β), and the step of mixing the component (Α) into the heated component (B) The method is suitable. The apparatus used in the step of melt-kneading the force (A) and the component (B) can be exemplified by a biaxial extruder, an experimental grade Brass _ machine (10) 〇 * foreign fine machine manufacturing plant (stock) manufacturing ), micro-experimental Brass weaving press (labo plast mi·丨). mUl miCr〇; Toyo Seiki Co., Ltd. (shares) one or two = press; homogenizer, τ κ. Division (ΡΙΊΠΠΧ) (share) manufacturing ) Waiting for the escrow, chemical ritual crying, Gu Guang (1) (cylinder tube) machine, ♦ stirring honing machine (. - ", machine, jet jet mixer, 朦体研君 (Fuji gold (share)) Registered 2 sound generator, high dust homogenizer, machine with bucket (red cylinder), etc.), static mixer, micro-mixer, etc., without the barrel, to the right, 1000 to 2500 seconds / 逑When the rate is generally 200 to (10) (10) seconds to the top left, the aqueous emulsion is preferably dried. The shear rate is 2 sec. &quot;The hardened material obtained by L\ has improved the adhesion of the 321925 (revision). Rain ^Please ί (9 9 years. 7 曰.年月卜· 201041645 VII. Patent application scope 1. An aqueous emulsion containing the following components (A), (B) and into (C): • Ingredient (A): containing α, /9-unsaturated a structural unit of a carboxylic acid, an alpha, azeo-unsaturated carboxylic acid derived from an aliphatic alcohol having from 1 to 10 carbon atoms having a substituent group and an α,/3-unsaturated carboxylic acid An acrylic resin having a structural unit of an acid ester, wherein the acrylic resin has a hydrophilic ratio of 9 to 12 (here, the hydrophilic ratio of the acrylic resin is a hydrophilic ratio of a monomer derived from a structural unit of the acrylic resin) The weight average, the hydrophilic ratio of the monomer is determined by the following formula: The hydrophilic ratio of the monomer = 20x (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer &quot;); B): thermoplastic polymer; component (C): water. 2. The aqueous emulsion according to claim 1, wherein the component (B) comprises: a thermoplastic polymer having a structural unit derived from ethylene and/or propylene. 3. The aqueous emulsion according to claim 1, wherein the component (B) comprises: in the structural unit derived from ethylene and/or propylene and from the formula (1) CH2=CH-R (I) In the copolymer of structural units of an acetamidine compound represented by R, a 2nd alkyl group, a 3rd alkyl group or an alicyclic hydrocarbon group, α,/5 -unsaturated 47 321925 (revision) 201041645 99109034 Patent Application (July 23, 1999) A copolymer obtained by graft polymerization of a carboxylic anhydride. '4. The aqueous emulsion according to claim 3, wherein the acetaminophen compound represented by the formula (I) is acetonitrile. The aqueous emulsion according to any one of claims 1 to 4, wherein the component (B) is MFR (190 ° C, 2.16 kgf) of 130 g/10 min or more, 300 g/10 min. The following thermoplastic polymers. 6. The aqueous emulsion according to any one of claims 1 to 5, wherein the aqueous emulsion is characterized in that the component (A) and the component (B) are dispersed and the component (C) is a dispersion medium. Wherein the volume-based median diameter of the dispersoid is from 0.01/zm to 3/zm. 7. The aqueous emulsion according to any one of claims 1 to 6, wherein the aliphatic alcohol having a carbon atom number of 1 to 10 V and the α,β-unsaturated source having an amine group capable of having a substituent The structural unit of the α,-unsaturated carboxylic acid ester derived from the carboxylic acid is a structural unit derived from cerium methacrylate or hydrazine-dimethylaminoethyl ester. The aqueous emulsion according to any one of claims 1 to 7, wherein the structural unit derived from the α,/5-unsaturated carboxylic acid is a structural unit derived from acrylic acid or mercaptoacrylic acid. A method for producing an aqueous emulsion, characterized in that after the component (Α) and the component (Β) are melt-kneaded, the obtained molten mixture is mixed with the component (C); the component (Α): contains α, stone- a structural unit of an unsaturated carboxylic acid, and an α, 10,000-unsaturated Wei derived from an aliphatic alcohol having 1 to 10 carbon atoms having a substituent group and an α,/9-unsaturated carboxylic acid An acrylic resin of a structural unit of an acid ester, wherein the acrylic acid is 48 321 925 (revision) 201041645 Patent Application No. 99109034 (July 23, 1999) The hydrophilic ratio of the resin is 9 to 12 (in Here, the hydrophilic ' ratio of the acrylic resin is the weight average of the hydrophilicity ratio of the monomer derived from the structural unit of the acrylic resin, and the hydrophilic ratio of the monomer is calculated by the following formula: The hydrophilic ratio of the monomer = 2 0 X (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer)); the component (B): the thermoplastic polymer; the component (C): water. Π u 10. A cured product obtained by drying an aqueous emulsion of any one of claims 1 to 8. 11. A laminate comprising: a substrate layer composed of at least one material selected from the group consisting of a wood material, a cellulose material, a plastic material, a ceramic material 1 and a metal material, and a patent application scope The layer formed by the hardened material of item 10. 12. A method of manufacturing a laminate comprising the steps of: q forming a base of at least one material selected from the group consisting of wood materials, cellulosic materials, plastic materials, ceramic materials, and metal materials. On the material layer, the aqueous emulsion of any one of claims 1 to 8 is coated to obtain a laminate having the substrate layer and the aqueous emulsion layer; and the laminate obtained in the above step is dried to obtain A step of providing a laminate of the above-mentioned base material layer and the cured layer obtained from the above aqueous emulsion. 13. An emulsifier comprising a structure comprising alpha, /3 -unsaturated ferulic acid 49 321 925 (revision) 201041645 patent application No. 99109034 (July 23, 1999) unit, and source free An acrylic resin having a structural group of an aliphatic group having 1 to 10 carbon atoms and a structural group derived from an α, a cold-unsaturated carboxylic acid ester derived from an a, /5-unsaturated carboxylic acid as an active ingredient And the hydrophilic ratio of the acrylic acid resin is from 9 to 12 (here, the hydrophilic ratio of the acrylic resin is a weight average of the hydrophilic ratio of the monomer from which the structural unit of the acrylic resin is derived, and the hydrophilicity of the monomer The ratio is a value calculated by the following formula: The hydrophilic ratio of the monomer = 20 χ (the amount of the hydrophilic portion of the monomer) / (the molecular weight of the monomer)). 14. The emulsifier according to claim 13, wherein the aliphatic alcohol having 1 to 10 carbon atoms and the α, /3-unsaturated carboxylic acid derived from the amino group having a substituent may be derived. The structural unit of the /3-saturated carboxylic acid ester is a structural unit derived from N,N-diguanidinoethyl methacrylate. 15. The emulsifier according to claim 13 or 14, wherein the structural unit derived from the α, /3-unsaturated carboxylic acid is derived from at least one selected from the group consisting of acrylic acid and methacrylic acid. Construction unit. 16. The use of an aqueous emulsion according to any one of claims 1 to 8 for grouping at least one selected from the group consisting of wood materials, cellulosic materials, plastic materials, ceramic materials, and metal materials A hardened layer is formed on the substrate layer formed of the material. 50 321925 (revision)